Modulating the Shape of Short Metal‐Mediated Heteroleptic Tapes of Porphyrins

In view of developing artificial light‐responsive complex systems, the preparation of discrete and robust heteroleptic assemblies of different chromophores in precisely defined positions is of great value since they would allow to investigate directional processes unavailable in symmetrical architec...

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Veröffentlicht in:Chemistry : a European journal 2023-06, Vol.29 (36), p.e202300893-n/a
Hauptverfasser: Vidal, Alessio, Rossato, Daniel, Iengo, Elisabetta, Balducci, Gabriele, Alessio, Enzo
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container_issue 36
container_start_page e202300893
container_title Chemistry : a European journal
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creator Vidal, Alessio
Rossato, Daniel
Iengo, Elisabetta
Balducci, Gabriele
Alessio, Enzo
description In view of developing artificial light‐responsive complex systems, the preparation of discrete and robust heteroleptic assemblies of different chromophores in precisely defined positions is of great value since they would allow to investigate directional processes unavailable in symmetrical architectures. Here we describe the preparation, through a modular stepwise approach, and characterization of four novel and robust metal‐mediated heteroleptic 4+3 porphyrin tapes, labeled D4−T4−D4, D3−T4−D3, D4−T3−D4, and D3−T3−D3, where a central meso‐tetrapyridylporphyrin (either 3′‐TPyP=T3 or 4′‐TPyP=T4) is connected to two equal cis‐dipyridylporphyrins (either 3′cisDPyMP=D3 or 4′cisDPyMP=D4) through four {t,c,c‐RuCl2(CO)2} fragments. Whereas D4−T4−D4 is flat, the tapes containing at least one 3′PyP, i. e. D3−T4−D3, D4−T3−D4, and D3−T3−D3, have unprecedented – and well defined – 3D geometries, and each exists in solution as a pair of stereoisomers in slow conformational equilibrium. The X‐ray molecular structures of two such conformers, the C‐shaped (D3−T4−D3)C and the z‐shaped (D4−T3−D4)z, were determined and are fully consistent with the solution NMR findings. As in a chemical conveyor belt, our stepwise synthetic approach afforded the four novel and robust metal‐mediated heteroleptic 4+3 porphyrin tapes D4−T4−D4, D3−T4−D3, D4−T3−D4, and D3−T3−D3, where a central meso‐tetrapyridylporphyrin (either 3′‐TPyP=T3, or 4′‐TPyP=T4) is connected to two equal cis‐dipyridylporphyrins (either 3′cisDPyMP=D3, or 4′cisDPyMP=D4) through four highly symmetrical {t,c,c‐RuCl2(CO)2} (Ru) fragments.
doi_str_mv 10.1002/chem.202300893
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subjects Chemistry
Chromophores
Complex systems
heteroleptic
metal-mediated self-assembly
Molecular structure
NMR
Nuclear magnetic resonance
porphyrinoids
Porphyrins
Robustness
ruthenium
stepwise synthesis
Stereoisomerism
Stereoisomers
title Modulating the Shape of Short Metal‐Mediated Heteroleptic Tapes of Porphyrins
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