Synthesis, Structure, and Reactivity of sp Carbon Chains with Bis(phosphine) Pentafluorophenylplatinum Endgroups: Butadiynediyl (C<sub>4</sub>) through Hexadecaoctaynediyl (C<sub>16</sub>) Bridges, and Beyond

Mohr, W.; Stähl, Jutta; Hampel, Frank; Gladysz, J. A.

doi:10.1002/chem.200204741

Cited by 145 publications

(251 citation statements)

References 86 publications

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“…We have therefore studied the effect of multideterminant (MD) Slater-Jastrow trial wave functions for excited, cationic, and anionic states of oligoynes with 4,6,8,10, and 24 carbon atoms as well as a supercell of polyyne composed of 8 primitive cells. The Slater determinants in the MD wave functions contained all the orbital occupancies that are degenerate at the single-particle level.…”

Section: B Qmc Calculationsmentioning

confidence: 99%

Quasiparticle and excitonic gaps of one-dimensional carbon chains

Mostaani

Monserrat

Drummond

et al. 2016

Phys. Chem. Chem. Phys.

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We report diffusion quantum Monte Carlo (DMC) calculations of the quasiparticle and excitonic gaps of hydrogen-terminated oligoynes and polyyne. The electronic gaps are found to be very sensitive to the atomic structure in these systems. We have therefore optimised the geometry of polyyne by directly minimising the DMC energy with respect to the lattice constant and the Peierlsinduced carbon-carbon bond-length alternation. We find the bond-length alternation of polyyne to be 0.136(2)Å and the excitonic and quasiparticle gaps to be 3.30(7) and 3.4(1) eV, respectively. The DMC zone-centre longitudinal optical phonon frequency of polyyne is 2084(5) cm −1 , which is consistent with Raman spectroscopic measurements for large oligoynes.

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Section: B Qmc Calculationsmentioning

confidence: 99%

Quasiparticle and excitonic gaps of one-dimensional carbon chains

Mostaani

Monserrat

Drummond

et al. 2016

Phys. Chem. Chem. Phys.

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“…[2] They are much more effective than most other types of unsaturated bridging ligands, which usually can be twisted out of conjugation. [2] The C x linkages also appear to be extend-A C H T U N G T R E N N U N G able to greater lengths [4][5][6] than in analogs with carbon-or silicon-based endgroups.…”

Section: Introductionmentioning

confidence: 99%

Coordination‐Driven Self‐Assembly, Structures, and Dynamic Properties of Diplatinum Hexatriynediyl and Butadiynediyl Complexes in which the sp Carbon Chains are Shielded by sp³ Carbon Chains: Towards Endgroup–Endgroup Interactions

Owen

Stähl

Hampel

et al. 2007

Chemistry A European J

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Sequential reactions of trans-(C6F5)(p-tol3P)2Pt(C[triple chemical bond]C)3SiEt3 (PtC6SiEt3) with nBu4N+ F(-) (THF/methanol), PtCl, KPF6/tBuOK, and CuCl give trans,trans-[(C6F5){(p-tol3P)2}Pt(C[triple chemical bond]C)3Pt{(Pp-tol3)2}(C6F5)] (PtC6Pt) in 95 % yield on multigram scales. Reactions of PtC6Pt and Ar2P(CH2)mPAr2 afford substitution products trans,trans-[(C6F5){(Ar2P(CH2)mPAr2)}Pt(C[triple chemical bond]C)3Pt{(Ar2P(CH2)mPAr2)}(C6F5)] (PtC6Pt-m/Ar; m/Ar=8/p-tol, 78 %; 10/Ph, 82 %; 11/Ph, 69 %; 12/Ph, 57 %; 14/p-tol, 57 %; 14/p-C6H4-tBu, 71 %), in which the diphosphines span the square planar platinum endgroups. An analogous reaction with PEt3 gives a tetrakis PEt3 complex Pt'C6Pt' (72 %). The crystal structures of PtC6Pt, Pt'C6Pt', PtC6Pt-10/Ph, PtC6Pt-11/Ph, and PtC6Pt-14/p-tol or solvates thereof are compared. In PtC6Pt, the endgroups can avoid van der Waals contact, and define angles of 0 degrees . In PtC6Pt-14/p-tol, the sp3 chains twist around the sp chain in a chiral double-helical motif, with an endgroup/endgroup angle of 189 degrees . The sp3 chains are too short to adopt analogous conformations in the other complexes, but laterally shield the sp chain. NMR spectroscopy shows that the helical enantiomers of PtC6Pt-14/p-tol rapidly interconvert in solution at low temperature. A crystal structure of PtC4Pt shows endgroups that are in van der Waals contact and define an angle of 41 degrees . Reactions with Ar2P(CH2)8PAr2 give PtC4Pt-8/Ar (Ar=Ph, 53 %; p-tol, 87 %). Low-temperature NMR spectroscopy establish non-helical chiral conformations. Electrochemical oxidations of the diplatinum complexes are analyzed, the reversibilities of which decrease with increasing sp chain length.

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“…Dodecain 1 hergestellt von Gladysz und Mitarbeitern. [217] Walton und Mitarbeiter synthetisierten tert-Butyl-funktionalisiertes Dodecain 2 [218] und das rekordverdächtige Oligoethinylen 4, welches durch UV-Spektroskopie identifiziert werden konnte. [219] Die extrem abgeschirmten Oligoethinylene 3 bis hin zum Decain [220] sowie die Nitril-geschützten Oligoethinylene 6 [221] wurden von Hirsch und Mitarbeitern synthetisiert.…”

Section: Elektrochemische Carbonisierung Perfluorierter Kohlenwassersunclassified

Nanostrukturierte Kohlenstoffmaterialien aus molekularen Vorstufen

et al. 2010

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Nanostrukturierte Kohlenstoffmaterialien, also Kohlenstoffe, die eine charakteristische Größe im Nanometerbereich sowie eine eventuell funktionalisierte Oberfläche aufweisen, spielen eine zentrale Rolle in vielen wissenschaftlichen Disziplinen. Erste Anwendungen finden derartige Materialien dabei unter anderem in Bereichen wie der Erforschung alternativer Energiequellen, leistungsfähiger Energiespeichermaterialien, nachhaltiger chemischer Technologien oder auch im Gebiet der organisch‐elektronischen Materialien. Des Weiteren könnten diese Materialien mögliche Ansätze und Lösungen bieten, um dem voranschreitenden Verbrauch fossiler Brennstoffe und somit dem Klimawandel entgegenzusteuern. Ferner könnten nanostrukturierte Kohlenstoffmaterialien auch auf dem Gebiet der Mikroelektronik einen Durchbruch herbeiführen. Allerdings ist die Entwicklung neuer Herstellungsverfahren für kohlenstoffreiche Materialien unabdingbar, die unter anderem Kontrolle über die Oberflächenchemie, die mesoskopische Struktur und die Mikrostruktur ermöglichen. Ein vielversprechender Ansatz ist dabei die Synthese dieser Materialien aus wohldefinierten molekularen Vorstufen.

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Synthesis, Structure, and Reactivity of sp Carbon Chains with Bis(phosphine) Pentafluorophenylplatinum Endgroups: Butadiynediyl (C₄) through Hexadecaoctaynediyl (C₁₆) Bridges, and Beyond

Cited by 145 publications

References 86 publications

Quasiparticle and excitonic gaps of one-dimensional carbon chains

Quasiparticle and excitonic gaps of one-dimensional carbon chains

Coordination‐Driven Self‐Assembly, Structures, and Dynamic Properties of Diplatinum Hexatriynediyl and Butadiynediyl Complexes in which the sp Carbon Chains are Shielded by sp³ Carbon Chains: Towards Endgroup–Endgroup Interactions

Nanostrukturierte Kohlenstoffmaterialien aus molekularen Vorstufen

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Synthesis, Structure, and Reactivity of sp Carbon Chains with Bis(phosphine) Pentafluorophenylplatinum Endgroups: Butadiynediyl (C4) through Hexadecaoctaynediyl (C16) Bridges, and Beyond

Cited by 145 publications

References 86 publications

Quasiparticle and excitonic gaps of one-dimensional carbon chains

Quasiparticle and excitonic gaps of one-dimensional carbon chains

Coordination‐Driven Self‐Assembly, Structures, and Dynamic Properties of Diplatinum Hexatriynediyl and Butadiynediyl Complexes in which the sp Carbon Chains are Shielded by sp3 Carbon Chains: Towards Endgroup–Endgroup Interactions

Nanostrukturierte Kohlenstoffmaterialien aus molekularen Vorstufen

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Synthesis, Structure, and Reactivity of sp Carbon Chains with Bis(phosphine) Pentafluorophenylplatinum Endgroups: Butadiynediyl (C₄) through Hexadecaoctaynediyl (C₁₆) Bridges, and Beyond

Coordination‐Driven Self‐Assembly, Structures, and Dynamic Properties of Diplatinum Hexatriynediyl and Butadiynediyl Complexes in which the sp Carbon Chains are Shielded by sp³ Carbon Chains: Towards Endgroup–Endgroup Interactions