Covalent Rigid-Rod Organometallic Polymers with Alternating Transition Metal Clusters and Conjugated Spacers in the Main Chain

Leoni, Piero; Marchetti, Lorella; Mohapatra, Swagat K.; Ruggeri, Giacomo; Ricci, Lucia Battaglia

doi:10.1021/om0604021

Cited by 19 publications

(5 citation statements)

References 19 publications

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“…145 Interesting rigid-rod polymers (55) containing alternating {Pt 6 } clusters and conjugated alkynyl moieties have been synthesized with molecular weights up to 148 000 g mol. 146 The UV-Vis absorption spectra of these complexes suggests that some electron delocalization along the backbone has been achieved. Pd-pincer complexes were also employed as a route to supramolecular cruciforms.…”

Section: Ferrocene-containing and Related Organometallic Polymersmentioning

confidence: 97%

Inorganic and organometallic polymers

Noonan¹,

Gates²

2007

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Section: Ferrocene-containing and Related Organometallic Polymersmentioning

confidence: 97%

Inorganic and organometallic polymers

Noonan¹,

Gates²

2007

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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“…Finally, interesting one‐dimensional molecular architectures comprising (i) hexa‐ and trinuclear Pt clusters separated by conjugated 1,4‐diethynylphenyl groups ( 135 , Scheme )114 or (ii) rigid‐rod polymers with alternating hexanuclear clusters and conjugated spacers115 were recently described.…”

Section: Future Trendsmentioning

confidence: 99%

Bridging and Terminal (Phosphanido)platinum Complexes

Mastrorilli¹

2008

Eur J Inorg Chem

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The PR2– group (the phosphanido group, according to the modern IUPAC rules) possesses a strong nucleophilicity, a high bridging tendency and a remarkable flexibility. This review addresses the issue of (phosphanido)platinum complexes, subdividing them into terminal and bridging species. Terminal (phosphanido)platinum complexes are usually prepared by deprotonation of a coordinated secondary (or primary) phosphane on a cationic PtII complex, by an appropriate base. The terminally bonded phosphanide group shows no tendency to form multiple bonds with platinum: in all crystallographically characterised Pt complexes, the terminal phosphanido P atom is pyramidal. Due to the high nucleophilicity granted by the presence of the active lone pair on P, terminal (phosphanido)platinum complexes react with molecules such as O2 and S8, and they can be used for the synthesis of dimetallic compounds upon reaction with suitable metal fragments. The known PtI phosphanido‐bridged complexes are dinuclear, diamagnetic and endowed with a strong Pt–Pt bond. The μ‐PPh2 bridge in PtI dimers arises often by (thermal) activation of the P–C bond in coordinated PPh3 or dppm. PtI phosphanido‐bridged complexes are also prepared by reaction of (dichlorido)platinum complexes with reagents such as Na, NaOH, alcohols. For such complexes a multifaceted reactivity, including the substitution of a terminal ligand, the reaction with electrophiles such as H+ and its isolobal analogues, the insertion into the μ‐P–Pt bond, has been reported. Hydridophosphanido complexes are formed by oxidative addition of a P–H bond onto zero‐valent Pt complexes, by protonation of PtI dimers or by action of BH4– on halido species. Dehydrochlorination of secondary (and primary) phosphane complexes gives chlorido complexes which are mostly prepared in the anti‐[(PRR′2)(Cl)Pt(μ‐PR″2)]2 geometry. Chiral complexes are obtained when asymmetric phosphanido P atoms are present in the molecule. A rich coordination chemistry has been developed on organometallic phosphanido Pt complexes bearing the pentafluorophenyl group. In this framework, a great number of Pt complexes of various nuclearity have been crystallographically characterised and their reactivity towards oxidants studied. The class of polynuclear phosphanido Pt complexes is represented by triangulo species, in which the bridging phosphanide group is typically μ‐PPh2 or μ‐PtBu2, by linear complexes of various nuclearity and by bent species stemming from the presence of a triply bridging diphenylphosphanido ligand in the molecule. Applications of phosphanido Pt complexes in catalysis and materials chemistry are also discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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“…16,17 Despite this interest, the physical properties of well-defined series of systematically varied metal-terminated OPEs are yet to be explored; although there have been a large number of reports of ligated-metal-capped 1,4-diethynylarenes (A, Chart 1), and their corresponding polymers (in which the ligated metals are in the repeat units: B, Chart 1), [43][44][45][46][47][48][49][51][52][53][54][55][56][57][58][59][60][61][62][63][64][65][66] there are considerably fewer reports of well-characterized "dimers" (C, Chart 1) [50][51][52]64,[67][68][69][70][71] or well-defined higher oligomers. Noteworthy series of the latter include (PhCtC){Pt-(PBu n 3 ) 2 (CtC-4-C 6 H 4 CtC)} n Pt(PBu n 3 ) 2 (CtCPh) (n=1-4, 6) from Schanze and co-workers 72,73 74 Excluding the "monomer" case (A, Chart 1), the literature for metal termination of OPEs is sparse, specific examples being (triphenylphosphine)gold and cluster-capped tri(phenyleneethynylene) 75 (D, Chart 1) and platinum-tri(aryleneethynylene) polymers (E, Chart 1). 76 Che and co-workers have reported the photophysical properties of (PCy 3 )Au-(CtC-4-C 6 H 4 ) n CtCAu(PCy 3 ) (n = 1-4), 77 and, particularly relevant to the present study, Klein et al have summarized the evolution of cyclic voltammetric, UV-vis-NIR spectroelectrochemical, IR spectroel...…”

Section: Introductionmentioning

confidence: 99%

Organometallic Complexes for Nonlinear Optics. 42. Syntheses, Linear, and Nonlinear Optical Properties of Ligated Metal-Functionalized Oligo(p-phenyleneethynylene)s

Dalton

Cifuentes²,

Watson³

et al. 2009

Inorg. Chem.

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A combination of UV-vis-NIR spectroscopy, femtosecond Z-scan measurements, and time-dependent density functional theory (TD-DFT) calculations have been used to comprehensively investigate the linear optical and nonlinear optical (NLO) properties of pi-delocalizable metal-functionalized oligo(phenyleneethynylene)s. A range of unsymmetrically or symmetrically end-functionalized mono-, di-, tri-, penta-, hepta-, and nona(phenyleneethynylene)s were synthesized, with larger examples bearing varying numbers of 2,5-di(hexyloxy)phenyl groups to ensure sufficient solubility of the metal complex derivatives. The effect of incorporating varying numbers of solubilizing substituents in the OPE bridge, peripheral group modification, OPE lengthening, coligand variation, and metal location in the OPE on the linear optical properties has been established, with the first three molecular modifications resulting in significant changes in the optical absorption maxima. TD-DFT calculations reveal that the most intense transition in the linear optical spectra is localized on the OPE bridge and involves excitation from acetylenic to cumulenic molecular orbitals that are not greatly spatially separated from one another. The nonlinear optical properties are dominated by two-photon absorption, which for all but 1,4-{trans-[RuCl(dppm)(2)]C[triple bond]C}(2)C(6)H(4) appears as a band around 11,400 cm(-1) and a sharp increase of nonlinear absorption at frequencies >17,000 cm(-1). Surprisingly, there is relatively little influence of the length of the OPE bridge on the magnitude of the two-photon absorption cross sections, which are in the range 300-1000 GM.

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Covalent Rigid-Rod Organometallic Polymers with Alternating Transition Metal Clusters and Conjugated Spacers in the Main Chain

Cited by 19 publications

References 19 publications

Inorganic and organometallic polymers

Inorganic and organometallic polymers

Bridging and Terminal (Phosphanido)platinum Complexes

Organometallic Complexes for Nonlinear Optics. 42. Syntheses, Linear, and Nonlinear Optical Properties of Ligated Metal-Functionalized Oligo(p-phenyleneethynylene)s

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