The pt-organometallic version of perigraniline: going blue.
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 C6 H4 and NCC2 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.
Contribution from Département de Chimie, Université de Sherbrooke, Sherbooke, PQ J1K 2R, Canada.
Tommy
T
Kenny
Shawkat M
SM
Aly
Gessie
G
Brisard
Daniel
D
Fortin
Pierre D
PD
Harvey
D000480:Alkynes / Q000737:chemistry*; D000880:Anthraquinones / Q000737:chemistry*; D018360:Crystallography, X-Ray; D055664:Electrochemical Techniques; D004735:Energy Transfer; D015394:Molecular Structure; D009944:Organoplatinum Compounds / Q000138:chemical synthesis*; D010720:Phosphines / Q000737:chemistry*; D010984:Platinum / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
D000480:Alkynes; D000880:Anthraquinones; D009944:Organoplatinum Compounds; D010720:Phosphines; D010984:Platinum