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The Pt‐Organometallic Version of Perigraniline: Going Blue
Author(s) -
Kenny Tommy,
Aly Shawkat M.,
Brisard Gessie,
Fortin Daniel,
Harvey Pierre D.
Publication year - 2013
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.201200741
Subject(s) - diimine , dihedral angle , chemistry , platinum , anthraquinone , steric effects , phenylacetylene , crystallography , photochemistry , stereochemistry , organic chemistry , catalysis , hydrogen bond , molecule
Four conjugated push–pull organometallic polymers ( [Pt]‐AQ ) n ( [Pt] = trans ‐bis(phenylacetylene)bis(tributylphosphine)platinum(II); AQ = 2‐bromo‐, 2,6‐dibromo‐, 2,6‐diamino‐, and unsubstituted anthraquinone diimine) were prepared and characterized by UV–vis spectroscopy and electrochemistry. A low‐energy charge transfer, CT, band ( [Pt] *→ AQ ; confirmed by density functional theory calculations), was found in the 445–500 nm window rather than the expected red‐shifted range above 630 nm. X‐ray structures of four model compounds reveal that steric hindrance induces large dihedral angles between the C 6 H 4 and NCC 2 planes, rendering π‐orbital overlap difficult between the [Pt] and AQ units. The position of the CT band is mainly driven the reduction potential of the anthraquinone diimine unit.