ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTInclusion of Organic Vapors by Crystalline, Solvatochromic [Pt(aryl isonitrile)4][Pd(CN)4] Compounds. "Vapochromic" Environmental SensorsChristopher L. Exstrom, John R. Jr. Sowa, Charles A. Daws, Daron Janzen, Kent Mann, Glenn Moore, and Frederick F. StewartCite this: Chem. Mater. 1995, 7, 1, 15–17Publication Date (Print):January 1995Publication History Published online1 May 2002Published inissue 1 January...

A series of new quinodimethane-substituted terthiophene and quaterthiophene oligomers has been investigated for comparison with a previously studied quinoid oligothiophene that demonstrated high mobilities ambipolar transport behavior in thin-film transistor devices. Each quinoidal thiophene derivative shows reversible one-electron oxidation between 0.85 1.32 V, quasi-reversible second 1.37 1.96 two-electron reduction −0.05 −0.23 V. The solution UV−vis−NIR spectrum each compound is dominated...

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTAn Electronic Nose Transducer Array of Vapoluminescent Platinum(II) Double SaltsSteven M. Drew, Daron E. Janzen, Carrie Buss, Daniel I. MacEwan, Kimberly Dublin, and Kent R. MannView Author Information Department Chemistry, 139 Smith Hall 207 Pleasant Street, SE, University Minnesota Minneapolis, 55455 Cite this: J. Am. Chem. Soc. 2001, 123, 34, 8414–8415Publication Date (Web):August 4, 2001Publication History Received12 April 2001Revised12...

The synthesis and metalation of two bis(phosphine)/dihydrosilyl ligands at rhodium(I) sources is reported. Irrespective the substitution silicon (diaryl versus diamino), multiple Si–H activations chloride migration afford tridentate bis(phosphine)/chlorosilyl complexes Rh(I). For diarylsilyl ligand, reaction with a cationic triflate precursor gives analogous triflatosilyl complex. [P2Si]H2 proligands their Rh provide distinct opportunities for exploring metal/silicon cooperative reactivity.

The synthesis and characterization of base-stabilized base-free pincer-type bis(phosphine)/silylene [P₂Si]Ru complexes are reported. complex performs cooperative, silylene-assisted hydride transfer to CO₂ CS₂.

Tricyanovinyl-capped oligothiophenes of up to six rings have been synthesized and characterized. The substituted oligomers display dramatic reductions in both their optical electrochemical band gaps comparison unsubstituted oligomers. solvatochromic behavior the terthiophene-substituted molecule was investigated a variety solvents. Stable oxidations were exhibited by sexithiophene-substituted on CV time scale. [structure: see text]

A unique trinuclear cluster containing two short Pt-->Ag dative bonds was prepared and characterized crystallographically. Two monocationic orthometalated Pt(II) complexes 2-phenylpyridine the tridentate ligand 9S3 (1,4,7-trithiacyclononane) exhibit axial sulfur interactions with Pt as well bonds. The bonding results in a dramatic shortening of Pt-S distance each complex cation, relative to mononuclear complex. Evidence for Pt-Ag solution is also presented.

A bis(phosphine)/triflatosilyl pincer-type Rh(i) complex can reversibly store one equivalent of H2 across the Si-Rh bond upon triflate migration from silicon to rhodium. The triflatosilyl serves as an effective precatalyst for norbornene hydrogenation, but Si-OTf cleavage is not implicated in major catalytic pathway. combined findings suggest possible strategies M/Si cooperation processes.

We report the synthesis and characterization of a new vapochromic platinum compound, [Pt(CN−cyclododecyl)4][Pt(CN)4]. This compound is stable to 120 °C reversibly sorbs three water molecules per formula unit at room temperature when it exposed 100% relative humidity. Dramatic changes in absorption emission spectra are observed response uptake. The vapor characteristics this material were further investigated by simultaneous optical reflectance quartz crystal microbalance (QCM) measurements,...

We analyze the electronic and molecular structures for ground excited states of aromatic terthiophene (3T), quinodimethane 3',4'-dibutyl-5,5' '-bis(dicyanomethylene)-5,5' '-dihydro-2,2':5',2' '-terthiophene (3Q), isologues with middle ring S-oxidized (3TO2, 3QO2). These represent extremes electron rich deficient states, often exhibiting complementary properties. Oxidizing central sulfur atom affects structure, affinity, photophysical properties both pi systems. The consequences 3T include...

We report the synthesis and full characterization for a series of cyclometallated complexes Pt(II) Pd(II) incorporating fluxional trithiacrown ligand 1,4,7-trithiacyclononane ([9]aneS3). Reaction [M(C insertion mark N)(micro-Cl)]2 (M = Pt(II), Pd(II); C N 2-phenylpyridinate (ppy) or 7,8-benzoquinolinate (bzq)) with [9]aneS3 followed by metathesis NH4PF6 yields N)([9]aneS3)](PF6). The P)([9]aneS3)](PF6) Cinsertion markP [CH2C6H4P(o-tolyl)2-C,P]-) were synthesized from their respective [Pt(C...

Rhodium(I) silylamide complexes supported by the 1,2-bis(di-tert-butylphosphino)ethane (dtbpe) ligand have been prepared and their structures reactivity studied. Although degrade over time to release corresponding silylamines, they react cleanly with silver(I) salts transfer amido group at ambient temperature. The bis(trimethylsilyl)amide complex (dtbpe)Rh–N(TMS)2 reacts CO2 form a carbamate that decomposes via loss of hexamethyldisiloxane bis(μ-isocyanate) dimer, suggesting silylamides may...

Preparation and characterization of a series pincer-type [P2Si]Co complexes are reported, including crystal structure the first base-free cobalt silylene complex. The cationic complex is strongly Lewis acidic oxophilic, readily coordinating bases such as triflate pyridine heterolytically cleaving O–H bonds in ethanol water.

A series of tricyanovinyl (TCV)-substituted oligothiophenes was synthesized and investigated with a number physical methods including UV/Vis, IR, Raman spectroscopy, nonlinear optical (NLO) measurements, X-ray diffraction, cyclic voltammetry. Mono- or disubstituted oligomers were prepared by the reaction tetracyanoethylene mono- dilithiated oligomers. The comparative effects symmetric asymmetric substitutions in electronic molecular properties have been addressed. These display dramatic...

A Pt(II) molecular square containing four fluxional trithiacrown ligands at the corners is prepared by transition metal-mediated self-assembly.

We report the synthesis and characterization of trans-Pt(p-CN−C6H4−C2H5)2(CN)2 compare properties to previously reported cis isomer, cis-Pt(p-CN−C6H4−C2H5)2(CN)2. These geometric isomers exhibit textbook differences in spectroscopic vapochromic properties, especially solid-state.

A three-channel cross-reactive sensor array based on vapoluminescent platinum(II) double salt materials has been characterized. Two arrays were studied, one consisting of [Pt(CN-cyclododecyl)4][Pt(CN)4] (1), [(phen)Pt(CN-cyclohexyl)2][Pt(CN)4] (2), and [Pt(CN-n-tetradecyl)4][Pt-(CN)4] (3) materials, where phen = 1,10-phenanthroline, a second that compound 3 replaced by the mixed material [(phen)Pt(CN-cyclododecyl)Cl)]2[(phen)Pt(CN-cyclododecyl)2]2[Pt(CN)4]3 (4). Compounds 2, 4 are...

Benzo[1,2-b:4,5-b']dithiophenes were oxidized under mild conditions with m-CPBA to yield the corresponding bis-sulfones (or tetraoxides). These sulfones possess red-shifted absorption and emission spectra relative parent molecules. Electrochemical analyses reveal that benzodithiophene molecules are transformed from electron donors acceptors.

Quinoidal-<italic>vs.</italic>-aromatic synergy: Cyclopentadithiophene-vinylene oligomers with different sizes, in oxidation states and as pro-aromatic quinoidals are studied considering balanced contributions of aromatic quinoidal forms.

Pincer-type [P2Si]Rh complexes featuring a rhodium–silicon bond are shown to facilitate well-defined stoichiometric reductions of CO2 with Si–O formation by two different pathways: (a) hydride transfer followed formate migration silicon, or (b) complete scission the C═O at Rh–Si unit afford product siloxide and carbonyl ligands. A combined experimental computational study shows that latter process occurs anomalous insertion into polarized Rhδ−–Siδ+ bond, finding is confirmed extending...

Abstract A metal/ligand cooperative approach to the reduction of small molecules by metal silylene complexes (R 2 Si=M) is demonstrated, whereby silicon activates incoming substrate and mediates net two‐electron transformations one‐electron redox processes at two centers. An appropriately tuned cationic pincer cobalt(I) complex, featuring a central donor, reacts with CO afford bimetallic siloxane, Co II centers, liberation CO; reaction complex ethylene yields similar product an bridge....

In this work, we report the stabilization of reduced states pyromellitic diimide by charge-balancing imide radical anions with cationic pyridinium groups attached to aromatic core. This structural modification is confirmed single-crystal X-ray diffraction analysis. Characterization (spectro)electrochemical experiments and computations reveal that addition an already electron-deficient ring system results in up +0.57 V shifts reduction potentials, largely as a consequence charge screening...