24 research outputs found
Synthesis and structural characterization of hexa-μ<sub>2</sub>-chlorido-μ<sub>4</sub>-oxido-tetrakis{[4-(phenylethynyl)pyridine-κN]copper(II)} dichloromethane monosolvate
In the crystal structure of the title compound, [Cu4Cl6O(C13H9N)4]·CH2Cl2, the core molecular structure consists of a Cu4 tetrahedron with a central interstitial O atom. Each edge of the Cu4 tetrahedron is bridged by a chlorido ligand. Each copper(II) cation is coordinated to the central O atom, two chlorido ligands and one N atom of the 4-phenylethynylpyridine ligand. In the crystal, the molecules are linked by intermolecular C - H⋯Cl interactions. Furthermore, C - H⋯π and π-π interactions also connect the molecules, forming a three-dimensional network. Hirshfeld surface analysis indicates that the most important contributions for the packing arrangement are from H⋯H and C⋯H/H⋯C interactions.</p
The Rise of Conjugated Poly-ynes and Poly(Metalla-ynes): From Design Through Synthesis to Structure-Property Relationships and Applications
Synthesis, optical spectroscopy, structural, and DFT studies on dimeric iodo-bridged Copper(I)complexes
Synthesis and structural characterization of hexa-μ<sub>2</sub>-chlorido-μ<sub>4</sub>-oxido-tetrakis{[4-(phenylethynyl)pyridine-κN]copper(II)} dichloromethane monosolvate
Two is Better Than One? Investigating the Effect of Incorporating Re(CO)<sub>3</sub>Cl Side-Chains into Pt(II) Diynes and Polyynes
Two is Better Than One? Investigating the Effect of Incorporating Re(CO)<sub>3</sub>Cl Side-Chains into Pt(II) Diynes and Polyynes
Pt(II) di-ynes and poly-ynes incorporating 5,5’- and 6,6’-disubstituted 2,2’-bipyridines were prepared following conventional Sonogashira and Hagihara dehydrohalogenation reaction protocols. Using Pt(II) dimers and polymers as a rigid-rod backbone, four new hetero-bimetallic compounds incorporating Re(CO)3Cl as a pendant functionality in the 2,2’-bipyridine core were obtained. The new hetero-bimetallic Pt-Re compounds were characterized by analytical and spectroscopic techniques. The solid state structures of a Re(I)-coordinated diterminal alkynyl ligand and a representative model compound were determined by single-crystal X-ray diffraction. Detailed photo-physical characterization of the hetero-bimetallic Pt(II) di-ynes and poly-ynes was carried out. We find that the incorporation of the Re(CO)3Cl pendant functionality in the 2,2’-bipyridine-containing main-chain Pt(II) di-ynes and poly-ynes has a synergistic effect on the optical properties, red shifting the absorption profile and introducing strong long-wavelength absorptions. The Re(I) moiety also introduces strong emission into the monomeric Pt(II) di-yne compounds, whereas this is suppressed in the poly-ynes. The extent of the synergy depends on the topology of the ligands. Computational modelling was performed to compare the energetic stabilities of the positional isomers and to understand the microscopic origin of the major optical absorptions. We find that 5,5’-disubstituted 2,2’-bipyridine systems are better candidates in terms of yield, photophysical properties and stability than their 6,6’-substituted counterparts. Overall, this work provides an additional synthetic route to control the photo-physical properties of metalla-ynes for a variety of optoelectronic applications
The impact of the alkyne substitution pattern and metalation on the photo-isomerization of azobenzene-based platinum(II) diynes and polyynes
Trimethylsilyl-protected
dialkynes incorporating azobenzene linker groups, Me<sub>3</sub>SiCCRCCSiMe<sub>3</sub> (R = azobenzene-3,3′-diyl, azobenzene-4,4′-diyl,
2,5-dioctylazobenzene-4,4′-diyl), and the corresponding terminal
dialkynes, HCCRCCH, have been synthesized and characterized.
The CuI-catalyzed dehydrohalogenation reaction between <i>trans</i>-[Ph(Et<sub>3</sub>P)<sub>2</sub>PtCl] and the deprotected dialkynes
in a 2:1 ratio in <sup>i</sup>Pr<sub>2</sub>NH/CH<sub>2</sub>Cl<sub>2</sub> gives the platinum(II) diynes <i>trans</i>-[Ph(Et<sub>3</sub>P)<sub>2</sub>PtCCRCCPt(PEt<sub>3</sub>)<sub>2</sub>Ph], while the dehydrohalogenation polycondensation reaction
between <i>trans</i>-[(<sup>n</sup>Bu<sub>3</sub>P)<sub>2</sub>PtCl<sub>2</sub>] and the dialkynes in a 1:1 molar ratio under
similar reaction conditions affords the platinum(II) polyynes, [−Pt(P<sup>n</sup>Bu<sub>3</sub>)<sub>2</sub>–CCRCC−]<sub><i>n</i></sub>. The materials have been characterized spectroscopically,
with the diynes also studied using single-crystal X-ray diffraction.
The platinum(II) diynes and polyynes are all soluble in common organic
solvents. Optical-absorption measurements show that the compounds
incorporating the <i>para</i>-alkynylazobenzene spacers
have a higher degree of electronic delocalisation than their <i>meta</i>-alkynylazobenzene counterparts. Reversible photoisomerization
in solution was observed spectroscopically for the alkynyl-functionalized
azobenzene ligands and, to a lesser extent, for the platinum(II) complexes.
Complementary quantum-chemical modeling was also used to analyze the
optical properties and isomerization energetics
Synthesis, characterization, and optoelectronic properties of phenothiazine-based organic co-poly-ynes
Dicopper(I) Complexes Incorporating Acetylide-functionalized Pyridinyl-based Ligands::Synthesis, Structural and Photovoltaic Studies
Heteroaryl incorporated
acetylide-functionalized pyridinyl ligands (<b>L1–L6</b>) with the general formula Py-CC-Ar (Py = pyridine and Ar
= <i>thiophene-2-yl</i>, 2,2′<i>-bithiophene]-5-yl</i>, 2,2′<i>:5</i>′,2″<i>-terthiophene]-5-yl</i>, <i>thieno[2,3-<i>b</i>]thiophen-2-yl</i>, <i>quinoline-5-yl</i>, <i>benzo[c][1,2,5]thiadiazole-5-yl</i>) have been synthesized by Pd(0)/Cu(I)-catalyzed cross-coupling reaction
of 4-ethynylpyridine and the respective heteroaryl halide. Ligands <b>L1–L6</b> were isolated in respectable yields and characterized
by microanalysis, IR spectroscopy, <sup>1</sup>H NMR spectroscopy,
and ESI-MS mass spectrometry. A series of dinuclear Cu(I) complexes <b>1</b>–<b>10</b> have been synthesized by reacting <b>L1–L6</b> with CuI and triphenylphosphine (PPh<sub>3</sub>) (<b>R1</b>) or with an anchored phosphine derivative, 4-(diphenylphosphino)
benzoic acid (<b>R2</b>)/2-(diphenylphosphino)benzenesulfonic
acid (<b>R3</b>), in a stoichiometric ratio. The complexes are
soluble in common organic solvents and have been characterized by
analytical, spectroscopic, and computational methods. Single-crystal
X-ray structure analysis confirmed rhomboid dimeric structures for
complexes <b>1</b>, <b>2</b>, <b>4</b>, and <b>5</b>, and a polymeric structure for <b>6</b>. Complexes <b>1</b>–<b>6</b> showed oxidation potential responses
close to 0.9 V vs Fc<sup>0/+</sup>, which were chemically irreversible
and are likely to be associated with multiple steps and core oxidation.
Preliminary photovoltaic (PV) results of these new materials indicated
moderate power conversion efficiency (PCE) in the range of 0.15–1.56%
in dye-sensitized solar cells (DSSCs). The highest PCE was achieved
with complex <b>10</b> bearing the sulfonic acid anchoring functionality
Data for "The Impact of the Alkyne Substitution Pattern and Metallation on the Photo-isomerization of Azobenzene-based Platinum(II) Di-ynes and Poly-ynes"
Data from the computational modelling described in the article "The Impact of the Alkyne Substitution Pattern and Metallation on the Photo-isomerization of Azobenzene-based Platinum(II) Di-ynes and Poly-ynes". Includes optimised molecular structures, vibrational frequencies, electronic excitation level, simulated infrared (IR) and absorption spectra, and assignments of the electronic transitions