Synthesis and characterization of new meso -substituted unsymmetrical metalloporphyrins

The synthesis and characterization of new meso-substituted unsymmetrical metalloporphyrins has been described. A new modified Adler method was used for the synthesis of two unsymmetrical porphyrins. Reactions of these unsymmetrical porphyrins with metal acetates afforded the corresponding metalloporphyrins in high yields with excellent purity. These porphyrins and their metal derivatives were characterized by spectroscopic methods. However, the copper complexes were further studied by ESR spectra and zinc complex by fluorescence spectrum.     

A scheme for rapid prediction of cooperativity in hydrogen bond chains of formamides,acetamides, and N‐methylformamides

A scheme is proposed in this article to predict the cooperativity in hydrogen bond chains of formamides, acetamides, and N‐methylformamides. The parameters needed in the scheme are derived from fitting to the hydrogen bonding energies of MP2/6‐31+G** with basis set superposition error (BSSE) correction of the hydrogen bond chains of formamides containing from two to eight monomeric units. The scheme is then used to calculate the individual hydrogen bonding energies in the chains of formamides containing 9 and 12 monomeric units, in the chains of acetamides containing from two to seven monomeric units, in the chains of N‐methylformamides containing from two to seven monomeric units. The calculation results show that the cooperativity predicted by the scheme proposed in this paper is in good agreement with those obtained from MP2/6‐31+G** calculations by including the BSSE correction, demonstrating that the scheme proposed in this article is reasonable. Based on our scheme, a cooperativity effect of almost 240% of the dimer hydrogen bonding energy in long hydrogen bond formamide chains, a cooperativity effect of almost 190% of the dimer hydrogen bonding energy in long hydrogen bond acetamide chains, and a cooperativity effect of almost 210% of the dimer hydrogen bonding energy in long hydrogen bond N‐methylformamide chains are predicted. The scheme is further applied to some heterogeneous chains containing formamide, acetamide, and N‐methylformamide. The individual hydrogen bonding energies in these heterogeneous chains predicted by our scheme are also in good agreement with those obtained from Møller‐Plesset calculations including BSSE correction. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Substituent effects in cooperativity of chalcogen bonds

In the present work, substituent effects on cooperativity of S···N chalcogen bonds are studied in XHS···NCHS···4-Z–Py (X = F, Cl; Z = H, F, OH, CH₃, NH₂, NO₂, and CN; and Py = pyridine) complexes using ab initio calculations. An increased attraction or a positive cooperativity is observed on introduction of a third molecule to the XHS···NCHS and NCHS···4-Z–Py binary systems. The shortening of each chalcogen bond distance in the ternary systems is dependent on the substituent Z and is increased in the order Z = NH₂ > OH > CH₃ > H > F > CN > NO₂. The electronic aspects of the complexes are analysed using molecular electrostatic potential, and the parameters derived from the atoms in molecules and natural bond orbital methodologies. According to interaction energy decomposition analysis, the electrostatic energies are important in the interaction energy of S···N bonds and may be regarded as being responsible for the stability of these complexes.     

Study on the Model for Regulation of the Allosteric Enzyme Activity

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Influence of cooperativity on the frequency shift of the Ar–H stretch vibration in HArF complexes

CH₃Li–FArH–X (X?=?H₂, OC, N₂, P₂, CO₂, CO, BeH₂) trimers have been investigated using quantum chemical calculations at the QCISD/6-311++G(2d,2p) level. The results show that the lithium bonding has a prominent effect on the strength and properties of the hydrogen bonding. The hydrogen-bonding interaction energy is increased by 160–340% due to the presence of lithium bonding. The Ar–H stretch vibration shows a blue shift in the FArH–X (X?=?H₂, OC, N₂, CO₂, CO) dimer, but a red shift in the FArH–X (X?=?P₂, BeH₂) dimer. The red shift is increased in the corresponding trimer, while the blue shift shows a different change. The blue shift is also increased in CH₃Li–FArH–X (X?=?H₂, OC, N₂, CO₂) trimers, but it changes to a red shift in the CH₃Li–FArH–CO trimer. The shift change is consistent with the explanation given by Joseph and Jemmis.     

Effect of substitution and cooperativity on the Cl–F blue shift in single-electron halogen-bonded H3C ··· ClF complex

The effect of substitution and cooperativity on the blue shift of Cl–F stretch vibration in H₃C ··· ClF complex has been studied with quantum chemical calculations at the UMP2(Full)/aug-cc-pVTZ level. The electron-withdrawing group (F atom) in the electron donor decreases the blue shift, whereas the electron-donating group (methyl group) in the electron donor cause it to increase. The cooperativity between two different types of halogen bonds in H₃C ··· ClF ··· ClF complex enhances the strength of single-electron halogen bond and the blue shift. The natural bond orbital (NBO) and atoms in molecules (AIM) analyses have been performed for the halogen-bonded complexes.     

Making and breaking of small water clusters: A combined quantum chemical and molecular dynamics approach

We present a combined quantum chemical and molecular dynamics study of cyclic and noncyclic water n-mers ([(H₂O]_n, n = 2–6) at four different temperatures and showcase that the dynamics of small water clusters can reproduce the known properties of bulk water reasonably well. We investigate the making and breaking of the water clusters by computing the hydrogen bond strengths, average lifetimes, and relative stabilities, which are important to understand the complex solution dynamics. We compare the behavior of water clusters in the gas phase and in the solution phase as well as the variation in the properties as a function of cluster size and highlight the notably more interesting cluster dynamics of the water trimer when compared to the other water clusters. © 2019 Wiley Periodicals, Inc.