2003
DOI: 10.1021/ja029564o
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Ligand Effects on Charge Transport in Platinum(II) Acetylides

Abstract: To investigate the electrical characteristics of organometallic complexes as molecular conductors, organometallic pi-conjugated molecules of the type trans-[PtL2(CCC6H4SAc-4)2], where L = PCy3, PBu3, PPh3, P(OEt)3, P(OPh)3, were synthesized and characterized by NMR, IR, UV, and X-ray spectroscopies. For the three complexes (L = PCy3, PPh3, and P(OEt)3) that could be measured using a cross-wire junction technique, the current-voltage (I-V) characteristics of a molecular monolayer of these complexes showed no li… Show more

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Cited by 158 publications
(101 citation statements)
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“…47 Despite the modest (0.08 eV) variation in the HOMO-LUMO gap as a function of the supporting ligand, L, the I-V characteristics of these filmbased junctions were also identical within experimental error. On the basis of these conductance results from both crossedwire thin-films of Schull and those from I(s) single-molecule based junctions of 1a and 1b described here, it could initially be concluded that the supporting ligands L play no significant role in the electrical characteristics of the junctions formed from trans-Pt(CuCR) 2 L 2 complexes.…”
Section: Resultsmentioning
confidence: 84%
See 1 more Smart Citation
“…47 Despite the modest (0.08 eV) variation in the HOMO-LUMO gap as a function of the supporting ligand, L, the I-V characteristics of these filmbased junctions were also identical within experimental error. On the basis of these conductance results from both crossedwire thin-films of Schull and those from I(s) single-molecule based junctions of 1a and 1b described here, it could initially be concluded that the supporting ligands L play no significant role in the electrical characteristics of the junctions formed from trans-Pt(CuCR) 2 L 2 complexes.…”
Section: Resultsmentioning
confidence: 84%
“…In contrast, analogous wire-like trans-bis (alkynyl) platinum complexes have been little explored in molecular junctions. [47][48][49] This is likely due to the perceptions of low conductivity arising from the smaller contribution of Pt (5d) orbitals to the frontier orbitals of square planar trans-Pt (CuCR) 2 L 2 (L = phosphine) complexes compared with the more extensive delocalisation in the HOMOs of octahedral complexes trans-M(CuCR) 2 L 4 (M = Fe, Ru, Os) along the π-d-π-conjugated molecular backbone. 45,[50][51][52][53] However, as discussed by McGrady in the context of pseudo-1D metal string complexes, efficient through-molecule conductance can be achieved through frontier orbitals which are distributed near, and energetically aligned with, the electrodes and need not be evenly distributed along the entire molecular backbone.…”
Section: Introductionmentioning
confidence: 99%
“…Specifically, we have demonstrated the utility of this technique to compare the conductivity of aliphatic and aromatic molecules (36) as well as aromatic and organometallic species (37). A crossed-wire tunneling junction is formed when one 10-m diameter Au wire, modified with a monolayer of the molecule of interest, is brought into gentle contact with a second unmodified Au wire controlled by a small dc deflection current in the presence of an external magnetic field.…”
Section: Molecular Junction Measurementsmentioning
confidence: 99%
“…[9] Although the charge transport in plat-A C H T U N G T R E N N U N G inum(II)-acetylides has been demonstrated, [17] solutionprocessible organometallic polymer semiconductors possessing donor-acceptor (D-A) architecture and platinum center in the backbone were recently shown to exhibit broad absorption bands due to the intramolecular charge transfer (ICT) between the donor and acceptor units and small bandgaps (even down to near-infrared) suitable for photovoltaic devices. [9] The complexation of an electron-rich platinum(II) ion into the conjugated chain was reported to enhance the intrachain charge transport of p-conjugated polymers.…”
mentioning
confidence: 99%