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271.
Flexible and Rigid Amine‐Functionalized Microporous Frameworks Based on Different Secondary Building Units: Supramolecular Isomerism,Selective CO2 Capture,and Catalysis 下载免费PDF全文
Ritesh Haldar Dr. Sandeep K. Reddy Venkata M. Suresh Dr. Sudip Mohapatra Prof. Sundaram Balasubramanian Prof. Tapas Kumar Maji 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(15):4347-4356
We report the synthesis, structural characterization, and porous properties of two isomeric supramolecular complexes of ([Cd(NH2?bdc)(bphz)0.5]?DMF?H2O}n (NH2?bdc=2‐aminobenzenedicarboxylic acid, bphz=1,2‐bis(4‐pyridylmethylene)hydrazine) composed of a mixed‐ligand system. The first isomer, with a paddle‐wheel‐type Cd2(COO)4 secondary building unit (SBU), is flexible in nature, whereas the other isomer has a rigid framework based on a μ‐oxo‐bridged Cd2(μ‐OCO)2 SBU. Both frameworks are two‐fold interpenetrated and the pore surface is decorated with pendant ?NH2 and ?N?N? functional groups. Both the frameworks are nonporous to N2, revealed by the type II adsorption profiles. However, at 195 K, the first isomer shows an unusual double‐step hysteretic CO2 adsorption profile, whereas the second isomer shows a typical type I CO2 profile. Moreover, at 195 K, both frameworks show excellent selectivity for CO2 among other gases (N2, O2, H2, and Ar), which has been correlated to the specific interaction of CO2 with the ?NH2 and ?N?N? functionalized pore surface. DFT calculations for the oxo‐bridged isomer unveiled that the ?NH2 group is the primary binding site for CO2. The high heat of CO2 adsorption (ΔHads=37.7 kJ mol?1) in the oxo‐bridged isomer is realized by NH2???CO2/aromatic π???CO2 and cooperative CO2???CO2 interactions. Further, postsynthetic modification of the ?NH2 group into ?NHCOCH3 in the second isomer leads to a reduced CO2 uptake with lower binding energy, which establishes the critical role of the ?NH2 group for CO2 capture. The presence of basic ?NH2 sites in the oxo‐bridged isomer was further exploited for efficient catalytic activity in a Knoevenagel condensation reaction. 相似文献
272.
The present study reports the shell thickness dependence fluorescence resonance energy transfer between Rhodamine 6G dye and Au@SnO2 core–shell nanoparticles. There is a pronounced effect on the PL quenching and shortening of the lifetime of the dye in presence of Au@SnO2 core–shell nanoparticles. The calculated energy transfer efficiencies from dye to Au@SnO2 are 64.4% and 78.3% for 1.5 nm and 2.5 nm thickness of shell, respectively. Considering the interactions of single acceptor and multiple donors, the calculated average distances (rn) are 75.8 and 71.5 Å for 1.5 nm and 2.5 nm thick core–shell Au@SnO2 nanoparticles, respectively. 相似文献
273.
Usharani Subuddhi Sourav Haldar S. Sankararaman Ashok K. Mishra 《Journal of photochemistry and photobiology. A, Chemistry》2008,200(2-3):381-387
The applicability of 1-(4-N,N-dimethylaminophenylethynyl)pyrene (DMAPEPy), a pyrene derivative showing intramolecular charge transfer, as a prospective probe for lipid bilayer membranes has been evaluated. High sensitivity of DMAPEPy to solvent polarity and viscosity makes it to act both as a polarity-sensitive probe and as a fluorescence anisotropy probe. The molecule shows high partition efficiency towards bilayer membranes in both solid gel as well as in the liquid crystalline phases. The emission spectrum, quenching experiment and lifetime data suggest bimodal distribution of DMAPEPy in the bilayer. Using the solvent polarity scales the polarity parameters of the two locations in lipid bilayer have been estimated. In the bilayer environment it exhibits remarkable spectral changes with temperature. The thermotropic phase change of the bilayer is sensitively monitored by fluorescence intensity as well as fluorescence anisotropy parameters. DMAPEPy is also capable of sensing the changes induced by membrane modifiers like cholesterol. 相似文献
274.
Krishna Kanta Haldar Dr. Tapasi Sen Sadananda Mandal Prof. Amitava Patra 《Chemphyschem》2012,13(17):3989-3996
We design well‐defined metal‐semiconductor nanostructures using thiol‐functionalized CdTe quantum dots (QDs)/quantum rods (QRs) with bovine serum albumin (BSA) protein‐conjugated Au nanoparticles (NPs)/nanorods (NRs) in aqueous solution. The main focus of this article is to address the impacts of size and shape on the photophysical properties, including radiative and nonradiative decay processes and energy transfers, of Au‐CdTe hybrid nanostructures. The red shifting of the plasmonic band and the strong photoluminescence (PL) quenching reveal a strong interaction between plasmons and excitons in these Au‐CdTe hybrid nanostructures. The PL quenching of CdTe QDs varies from 40 to 86 % by changing the size and shape of the Au NPs. The radiative as well as the nonradiative decay rates of the CdTe QDs/QRs are found to be affected in the presence of both Au NPs and NRs. A significant change in the nonradiative decay rate from 4.72×106 to 3.92×1010 s?1 is obtained for Au NR‐conjugated CdTe QDs. It is seen that the sizes and shapes of the Au NPs have a pronounced effect on the distance‐dependent energy transfer. Such metal‐semiconductor hybrid nanostructures should have great potentials for nonlinear optical properties, photovoltaic devices, and chemical sensors. 相似文献
275.
Bhaumik C Das S Maity D Baitalik S 《Dalton transactions (Cambridge, England : 2003)》2012,41(8):2427-2438
Homo- and heteroleptic bis-tridentate ruthenium(II) and osmium(II) complexes of compositions [(tpy-PhCH(3))Ru(tpy-HImzPh(3))](ClO(4))(2) (1), [(H(2)pbbzim)Ru(tpy-HImzPh(3))] (ClO(4))(2) (2) and [M(tpy-HImzPh(3))(2)](ClO(4))(2) [M = Ru(II) (3) and Os(II) (4)], where tpy-PhCH(3) = p-methylphenyl terpyridine, H(2)pbbzim = 2,6-bis(benzimidazole-2-yl)pyridine and tpy-HImzPh(3) = 4'-[4-(4,5-diphenyl-1H-imidazol-2-yl)-phenyl]-[2,2':6',2']terpyridine, have been synthesized and characterized by using standard analytical and spectroscopic techniques. These compounds were designed to increase the room temperature excited-state lifetimes of bisterpyridine-type ruthenium(II) and osmium(II) complexes. The X-ray crystal structures of two homoleptic complexes 3 and 4 have been determined and show that both the compounds crystallized in orthorhombic form with space group Fddd. The photophysical and redox properties of the complexes have been thoroughly investigated. All the complexes display moderately strong luminescence at room temperature with lifetimes in the range of 6-35 ns. The complexes are found to undergo one reversible oxidation in the positive potential window (0 to +1.6 V) and one irreversible and two successive quasi-reversible reductions in the negative potential window (0 to -2.0 V). The influence of solvents on the photophysical properties of the complexes has also been investigated in detail. 相似文献
276.
277.
Jude KM Banerjee AL Haldar MK Manokaran S Roy B Mallik S Srivastava DK Christianson DW 《Journal of the American Chemical Society》2006,128(9):3011-3018
The atomic-resolution crystal structures of human carbonic anhydrases I and II complexed with "two-prong" inhibitors are reported. Each inhibitor contains a benzenesulfonamide prong and a cupric iminodiacetate (IDA-Cu(2+)) prong separated by linkers of different lengths and compositions. The ionized NH(-) group of each benzenesulfonamide coordinates to the active site Zn(2+) ion; the IDA-Cu(2+) prong of the tightest-binding inhibitor, BR30, binds to H64 of CAII and H200 of CAI. This work provides the first evidence verifying the structural basis of nanomolar affinity measured for two-prong inhibitors targeting the carbonic anhydrases. 相似文献
278.
Wun-Chang Pan Dr. Carina Mützel Dr. Soumyajyoti Haldar Hendrik Hohmann Prof. Dr. Stefan Heinze Prof. Dr. Jeffrey M. Farrell Prof. Dr. Ronny Thomale Prof. Dr. Matthias Bode Prof. Dr. Frank Würthner Dr. Jing Qi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(15):e202400313
Replacement of sp2-hybridized carbon in polycyclic aromatic hydrocarbons (PAHs) by boron affords electron-deficient π-scaffolds due to the vacant pz-orbital of three-coordinate boron with the potential for pronounced electronic interactions with electron-rich metal surfaces. Using a diboraperylene diborinic acid derivative as precursor and a controlled on-surface non-covalent synthesis approach, we report on a self-assembled chiral supramolecular kagome network on an Ag(111) surface stabilized by intermolecular hydrogen-bonding interactions at low temperature. Scanning tunneling microscopy (STM) and spectroscopy (STS) reveal a flat band at ca. 0.33 eV above the Fermi level which is localized at the molecule center, in good agreement with tight-binding model calculations of flat bands characteristic for kagome lattices. 相似文献