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EP-4737521-A1 - AZA-METAL-DIPYRROMETHENE DERIVATIVES, PROCESSES OF PRODUCTION AND USES THEREOF AS PHOTOCATALYSTS

EP4737521A1EP 4737521 A1EP4737521 A1EP 4737521A1EP-4737521-A1

Abstract

The present invention concerns aza-metal-dipyrromethene derivatives, processes of production and uses thereof in photocatalysis.

Inventors

  • BEILLARD, Audrey
  • Bodio, Ewen
  • Godard, Amélie
  • CAVE, CHARLOTTE

Assignees

  • Centre National de la Recherche Scientifique
  • Université de Bourgogne

Dates

Publication Date
20260506
Application Date
20241031

Claims (13)

  1. A compound of following formula (I): wherein: M is a metal chosen from transition metals, post-transition metals and lanthanides, M being different from bore; A and B are independently chosen from: - H, - halogens, in particular F, Cl, Br and I, - CF 3 , - linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, possibly interrupted by at least one -O- or -NR- atom, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl, - linear, branched and cyclic (C 2 -C 12 )-alkynyl groups, optionally substituted by a NR a R b or N + R a R b R c group, wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole; said group being for example a dialkylpropargylamine or a trialkylpropargylammonium, - linear, branched and cyclic (C 2 -C 12 )-alkenyl groups, OR, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl, - NR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, - Aryl and heteroaryl groups, said groups being optionally substituted by at least one R 1 group chosen from: o halogens, in particular F, Cl, Br and I, o CF 3 , o N 3 , o OR, wherein R is chosen from linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and CH 2 -COOR a , wherein R a is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, possibly interrupted by at least one -O- or -NR- atom, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl, o NR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, o N + R a R b R c , wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, o S + R a R b R c , wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o COO - and COOR, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o P + R a R b R c , P(=O)(OR a )(OR b ), P(=O)(OR a )(O - ), and PO 3 2- , wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o N=CR a R b and CR a =NR b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o SO 3 H or SO 3 - ; W 1 and W 2 are independently chosen from: - linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, - linear, branched and cyclic (C 2 -C 12 )-alkynyl groups, optionally substituted by a NR a R b or N + R a R b R c group, wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole; said group being for example a dialkylpropargylamine or a trialkylpropargylammonium, - linear, branched and cyclic (C 2 -C 12 )-alkenyl groups, Aryl and heteroaryl groups, said groups being optionally substituted by at least one R 1 group chosen from: o linear, branched and cyclic (C 1 -C 12 )-alkyl groups, o halogens, in particular F, Cl, Br and I, o CF 3 , ∘ N 3 , o OR, wherein R is chosen from linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl, and CH 2 -COOR a , wherein R a is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, possibly interrupted by at least one -O- or -NR- atom, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl, o NR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, o N + R a R b R c , wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, o CH 2 -E, said group being in particular a phenyl group, more particularly a phenyl substituted by a R 1 group in para, wherein E is a group chosen from: ▪ NR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, ▪ N + R a R b R c , wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, ▪ S + R a R b R c , wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, ▪ P(=O)(OR a )(OR b ), P(=O)(OR a )(O - ), and PO 3 2- , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, ▪ C≡CR a , wherein R a is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, ▪ N=CR a R b and CR a =NR b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, ▪ PR a R b wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, ▪ P + R a R b R c wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, ▪ COO - and COOH, ▪ OH or O - , ▪ SO 3 H or SO 3 - , said optionally substituted heteroaryl being for example a pyridinium; X 1 and X 2 are independently chosen from; - Aryl groups, - Aryl groups being substituted, in particular at least in ortho or meta, by at least one R 2 group chosen from: o OH or O - group, o C≡CR a , wherein R a is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o CF 3 , ∘ N 3 , o OR, wherein R is chosen from linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl, and CH 2 -COOR a , wherein R a is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, interrupted by at least one -O- or -NR- atom, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl, o SH or S - group, o NR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, o COO - and COOR, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, R being in particular hydrogen, o CONR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o PR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o P + R a R b R c , wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o P(=O)(OR a )(OR b ), P(=O)(OR a )(O - ), and PO 3 2- , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o CH=N-NH 2 , and CH=N-NHR', wherein R' is chosen from linear, branched and cyclic (C 1 -C 12 )-alkyl groups, C(=S)NH 2 and C(=O)NH 2 , o SO 3 H or SO 3 - , - Heteroaryl groups, for example pyridine, pyrrole, thiazole, triazole, imidazole or thiophene, being optionally substituted, in particular at least in alpha or beta with the carbon of X 1 or X 2 that is bound to the rest of the compound of formula (I), by at least one R 2 group chosen from: o linear, branched and cyclic (C 1 -C 12 )-alkyl groups, o OH or O - group, o C≡CR a , wherein R a is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o CF 3 , ∘ N 3 , o OR, wherein R is chosen from linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl, and CH 2 -COOR a , wherein R a is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, interrupted by at least one -O- or -NR- atom, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl, o SH or S - group, o NR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, o COO - and COOR, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, R being in particular hydrogen, o CH 2 -COO - and CH 2 -COOR, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, R being in particular hydrogen, said group being for example pyrrolyl being N-substituted by CH 2 -COO - or CH 2 -COOH, o PR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o P + R a R b R c , wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o P(=O)(OR a )(OR b ), P(=O)(OR a )(O - ), and PO 3 2- , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o CH=N-NH 2 , and CH=N-NHR', wherein R' is chosen from linear, branched and cyclic (C 1 -C 12 )-alkyl groups, C(=S)NH 2 and C(=O)NH 2 , o SO 3 H or SO 3 - , said optionally substituted heteroaryl being for example a pyridinium, said heteroaryl groups being in particular heteroaryl groups, more particularly unsubstituted heteroaryl groups, comprising at least one N, O or S atom which is in alpha with the carbon of X 1 or X 2 that is bound to the rest of the compound of formula (I), said heteroaryl being for example a 2-pyridyl group, - C(Q 1 )(Q 2 )-Q, wherein: o Q is (CH 2 ) n -Q', wherein n is 0, 1 or 2, and Q' is chosen from X 1 as defined above, in particular pyridinyl, C(=O)H, C(=O)R a , COOR a and CONR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o Q 1 and Q 2 are chosen from linear, branched and cyclic (C 1 -C 12 )-alkyl groups, aryl groups, halogens, in particular F, and Q as defined above, at least one of Q 1 and Q 2 being chosen from linear, branched and cyclic (C 1 -C 12 )-alkyl groups, aryl groups, and halogens, in particular F, or A and W 1 , and/or B and W 2 form together a fused arene, in particular a fused benzene, said arene being optionally substituted as defined above about W 1 and/or W 2 , or A and Xi, and/or B and X 2 form together a fused arene, in particular a fused phenanthrene, said arene being optionally substituted as defined above about X 1 and/or X 2 , with the proviso that: - At least one of X 1 and X 2 is a substituted aryl at least in ortho by at least one R 2 group as defined above, or a heteroaryl group comprising at least one N, O or S atom which is adjacent to the carbon of X 1 or X 2 that is bound to the rest of the compound of formula (I), and - When X 1 and X 2 are both 2-pyrrolyl, 2-thiophenyl, or 5-oxazolyl, at least one of W 1 and W 2 is not alkyl; said compound of formula (I) being different from: with M being Al or Ga; with M being Al, Ga or In, and
  2. The compound according to claim 1, wherein A and B are H.
  3. The compound according to anyone of the preceding claims, wherein W 1 and W 2 are independently chosen from aryl and heteroaryl groups, said groups being optionally substituted by at least one R 1 as defined in claim 1, in particular at least in para position.
  4. The compound according to anyone of the preceding claims, wherein X 1 and X 2 are independently chosen from aryl groups being substituted, at least in ortho, by at least one R 2 group as defined in claim 1, and heteroaryl groups optionally substituted as defined in claim 1, comprising at least one N, O or S atom which is adjacent to the carbon of X 1 or X 2 that is bound to the rest of the compound of formula (I), said heteroaryl being for example a 2-pyridyl group.
  5. The compound according to anyone of the preceding claims, wherein M is chosen from transition metals and post-transition metals, in particular from transition metals.
  6. The compound according to anyone of the preceding claims, wherein M is chosen from Co, Cu, Ru, Pd, Ir, Au, In, Ga, Ti, Zr, Mn, Zn, Pt, Os, and Al.
  7. The compound according to anyone of the preceding claims, wherein M is not Al Ga, or In.
  8. The compound according to anyone of the preceding claims, wherein the coordination sphere of M is not completed with a ligand being pyridine.
  9. The compound according to anyone of the preceding claims, wherein W 1 and W 2 are not both Ph or substituted Ph, in particular in para, with R 1 being OMe, NMe 2 , or Me.
  10. The compound according to anyone of the preceding claims, wherein X 1 and X 2 are not both Ph substituted, in particular in ortho, with OH or O-.
  11. Use as a photocatalyst of a compound of following formula (II): wherein: M is a metal chosen from transition metals, post-transition metals and lanthanides, M being different from bore; A and B are independently chosen from: - H, - halogens, in particular F, Cl, Br and I, - CF 3 , - linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, possibly interrupted by at least one -O- or -NR- atom, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl, - linear, branched and cyclic (C 2 -C 12 )-alkynyl groups, optionally substituted by a NR a R b or N + R a R b R c group, wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole; said group being for example a dialkylpropargylamine or a trialkylpropargylammonium, - linear, branched and cyclic (C 2 -C 12 )-alkenyl groups, OR, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl, - NR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, - Aryl and heteroaryl groups, said groups being optionally substituted by at least one R 1 group chosen from: o halogens, in particular F, Cl, Br and I, o CF 3 , ∘ N 3 , o OR, wherein R is chosen from linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and CH 2 -COOR a , wherein R a is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, possibly interrupted by at least one -O- or -NR- atom, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl, o NR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, o N + R a R b R c , wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, o S + R a R b R c , wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o COO - and COOR, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o P + R a R b R c , P(=O)(OR a )(OR b ), P(=O)(OR a )(O - ), and PO 3 2- , wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o N=CR a R b and CR a =NR b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o SO 3 H or SO 3 - ; W 1 and W 2 are independently chosen from: - linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, - linear, branched and cyclic (C 2 -C 12 )-alkynyl groups, optionally substituted by a NR a R b or N + R a R b R c group, wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole; said group being for example a dialkylpropargylamine or a trialkylpropargylammonium, - linear, branched and cyclic (C 2 -C 12 )-alkenyl groups, Aryl and heteroaryl groups, said groups being optionally substituted by at least one R 1 group chosen from: o linear, branched and cyclic (C 1 -C 12 )-alkyl groups, o halogens, in particular F, Cl, Br and I, o CF 3 , ∘ N 3 , o OR, wherein R is chosen from linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl, and CH 2 -COOR a , wherein R a is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, possibly interrupted by at least one -O- or -NR- atom, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl, o NR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, o N + R a R b R c , wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, o S + R a R b R c , wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, o P(=O)(OR a )(OR b ), P(=O)(OR a )(O - ), and PO 3 2- , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o C≡CR a , wherein R a is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o N=CR a R b and CR a =NR b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o PR a R b wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o P + R a R b R c wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o COO - and COOH, o OH or O - , o SO 3 H or SO 3 - , o CH 2 -E, said group being in particular a phenyl group, more particularly a phenyl substituted by a R 1 group in para, wherein E is a group chosen from: ▪ NR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, ▪ N + R a R b R c , wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, ▪ S + R a R b R c , wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, ▪ P(=O)(OR a )(OR b ), P(=O)(OR a )(O - ), and PO 3 2- , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, ▪ C≡CR a , wherein R a is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, ▪ N=CR a R b and CR a =NR b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, ▪ PR a R b wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, ▪ P + R a R b R c wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, ▪ COO - and COOH, ▪ OH or O', ▪ SO 3 H or SO 3 - , said optionally substituted heteroaryl being for example a pyridinium; X 1 and X 2 are independently chosen from; - Aryl groups, - Aryl groups being substituted, in particular at least in ortho or meta, by at least one R 2 group chosen from: o OH or O - group, o C≡CR a , wherein R a is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o CF 3 , ∘ N 3 , o OR, wherein R is chosen from linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl, and CH 2 -COOR a , wherein R a is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, interrupted by at least one -O- or -NR- atom, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me,, and (hetero)aryl groups, in particular phenyl, o SH or S - group, o NR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, o COO - and COOR, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, R being in particular hydrogen, o CONR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o PR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o P + R a R b R c , wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o P(=O)(OR a )(OR b ), P(=O)(OR a )(O - ), and PO 3 2- , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o CH=N-NH 2 , and CH=N-NHR', wherein R' is chosen from linear, branched and cyclic (C 1 -C 12 )-alkyl groups, C(=S)NH 2 and C(=O)NH 2 , o SO 3 H or SO 3 - , - Heteroaryl groups, for example pyridine, pyrrole, thiazole, triazole, imidazole or thiophene, being optionally substituted, in particular at least in alpha or beta with the carbon of X 1 or X 2 that is bound to the rest of the compound of formula (I), by at least one R 2 group chosen from: o linear, branched and cyclic (C 1 -C 12 )-alkyl groups, o OH or O - group, o C≡CR a , wherein R a is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o CF 3 , ∘ N 3 , o OR, wherein R is chosen from linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl,and CH 2 -COOR a , wherein R a is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, interrupted by at least one -O- or -NR- atom, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl, o SH or S - group, o NR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, or R a and R b form together an heteroarene, in particular a carbazole, o COO - and COOR, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, R being in particular hydrogen, o CH 2 -COO - and CH 2 -COOR, wherein R is chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, R being in particular hydrogen, said group being for example pyrrolyl being N-substituted by CH 2 -COO - or CH 2 -COOH, o PR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o P + R a R b R c , wherein R a , R b and R c are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o P(=O)(OR a )(OR b ), P(=O)(OR a )(O - ), and PO 3 2- , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o CH=N-NH 2 , and CH=N-NHR', wherein R' is chosen from linear, branched and cyclic (C 1 -C 12 )-alkyl groups, C(=S)NH 2 and C(=O)NH 2 , o SO 3 H or SO 3' , said optionally substituted heteroaryl being for example a pyridinium, said heteroaryl groups being in particular heteroaryl groups, more particularly unsubstituted heteroaryl groups, comprising at least one N, O or S atom which is in alpha with the carbon of X 1 or X 2 that is bound to the rest of the compound of formula (I), said heteroaryl being for example a 2-pyridyl group, - C(Q 1 )(Q 2 )-Q, wherein: o Q is (CH 2 ) n -Q', wherein n is 0, 1 or 2, and Q' is chosen from X 1 as defined above, in particular pyridinyl, C(=O)H, C(=O)R a , COOR a and CONR a R b , wherein R a and R b are independently chosen from hydrogen, linear, branched and cyclic (C 1 -C 12 )-alkyl groups, and (hetero)aryl groups, in particular phenyl, o Q 1 and Q 2 are chosen from linear, branched and cyclic (C 1 -C 12 )-alkyl groups, aryl groups, halogens, in particular F, and Q as defined above, at least one of Q 1 and Q 2 being chosen from linear, branched and cyclic (C 1 -C 12 )-alkyl groups, aryl groups, and halogens, in particular F, or A and W 1 , and/or B and W 2 form together a fused arene, in particular a fused benzene, said arene being optionally substituted as defined above about W 1 and/or W 2 , or A and Xi, and/or B and X 2 form together a fused arene, in particular a fused phenanthrene, said arene being optionally substituted as defined above about X 1 and/or X 2 ,
  12. Process of photocatalysis comprising a step of irradiation of a reaction mixture comprising a compound of formula (II) as defined in claim 11.
  13. Process according to claim 12, wherein the irradiation is performed with red and/or near infrared light, in particular with a wavelength from 620 to 2000 nm, more particularly from 650 to 810 nm.

Description

The present invention concerns aza-metal-dipyrromethene derivatives, processes of production and uses thereof in photocatalysis. Photocatalysis is a process that uses light to accelerate a chemical reaction in the presence of a catalyst. This method is for example significant in environmental and energy applications. One of the primary advantages of photocatalysis is its environmental friendliness. It can for example degrade a wide variety of pollutants, including organic compounds, dyes, without producing harmful by-products. This makes it an excellent choice for wastewater treatment and air purification. Additionally, photocatalysis operates under mild conditions, typically at room temperature and atmospheric pressure, which reduces energy consumption and operational costs. And photocatalysis can also be used to carry out organic synthesis and therefore produce high-value-added molecules. Overall, photocatalysis stands out for its versatility, efficiency, and sustainability. At present, most of the used photocatalysts require activation by high-energy light irradiation (i.e. short wavelengths corresponding to the ultra-violet, violet and blue ranges). However, such irradiation has extremely low penetration of the reaction media (a few millimetres at most) and severely limits the dimensions of the synthesis reactors that can be used. In addition, this highly energetic radiation can cause damage to the reaction medium and even to the photocatalyst itself. There are a few examples of molecules or complexes that absorb in the red and/or NIR and are used as photocatalysts (for instance osmium complexes and organic catalysts). However, their stability, photostability and/or molar absorption coefficient are relatively limited in the red and even more so in the NIR. Accordingly, it is an object of the present invention to provide compounds that absorb intensely in the red and/or near infrared (NIR). Indeed, it has been underlined, for example, that going from a wavelength of 450 mm (blue) to 750 mm (the NIR range) can increase the photocatalysis reaction volume by a factor of 250 with increase of yield. This responds to the various issues involved in scaling up photocatalysis reactions. In addition, NIR radiation has a very low risk of damaging the reaction medium (e.g. use in medical imaging), even in case of a sensitive one. Another goal of the present invention is to provide complexes exhibiting intense absorptions that can exceed 60,000; 70,000 or 100,000 M-1cm-1 at wavelengths ranging from 680 to over 810 mm. These exceptional absorbances achieved by the compounds of the invention promote excellent activity at long wavelengths, even over short periods of time. By way of comparison, osmium complexes of the prior art have an absorbance more than 200 times lower at 740 mm and zero at 800 mm. Another goal of the present invention is to provide complexes that are tunable in terms of working wavelength, and therefore adjustable to the aimed reactor volume and material (lamp wavelength), but also in terms of the redox potential value (to adapt to the nature of the chemical reaction to catalyse), solubility and whether the catalysis is homogeneous or supported. Another goal of the present invention is to provide complexes resistant to photobleaching, which means they can be irradiated for prolonged periods without any risk of damage or degradation. This advantage is key to recycle the photocatalyst without loss of activity. The present invention thus relates to a compound of following formula (I): wherein: M is a metal chosen from transition metals, post-transition metals and lanthanides, M being different from bore; A and B are independently chosen from: H,halogens, in particular F, Cl, Br and I,CF3,linear, branched and cyclic (C1-C12)-alkyl groups, in particular Me, possibly interrupted by at least one -O- or -NR- atom, wherein R is chosen from hydrogen, linear, branched and cyclic (C1-C12)-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl,linear, branched and cyclic (C2-C12)-alkynyl groups, optionally substituted by a NRaRb or N+RaRbRc group, wherein Ra, Rb and Rc are independently chosen from hydrogen, linear, branched and cyclic (C1-C12)-alkyl groups, and (hetero)aryl groups, in particular phenyl, or Ra and Rb form together an heteroarene, in particular a carbazole; said group being for example a dialkylpropargylamine or a trialkylpropargylammonium,linear, branched and cyclic (C2-C12)-alkenyl groups, OR, wherein R is chosen from hydrogen, linear, branched and cyclic (C1-C12)-alkyl groups, in particular Me, and (hetero)aryl groups, in particular phenyl,NRaRb, wherein Ra and Rb are independently chosen from hydrogen, linear, branched and cyclic (C1-C12)-alkyl groups, and (hetero)aryl groups, in particular phenyl, or Ra and Rb form together an heteroarene, in particular a carbazole,Aryl and heteroaryl groups, said groups being optionally substituted by at least one R1 group chosen from