scholarly journals Intra-/Intermolecular Bifurcated Chalcogen Bonding in Crystal Structure of Thiazole/Thiadiazole Derived Binuclear (Diaminocarbene)PdII Complexes

Crystals ◽  
2018 ◽  
Vol 8 (3) ◽  
pp. 112 ◽  
Author(s):  
Alexander Mikherdov ◽  
Alexander Novikov ◽  
Mikhail Kinzhalov ◽  
Andrey Zolotarev ◽  
Keyword(s):  
Solid State ◽  
Crystal Packing ◽  
Topological Analysis ◽  
Molar Ratio ◽  
Aim Analysis ◽  
Aim Method ◽  
One Dimensional ◽  
Polymeric Chains ◽  
Non Covalent Interactions ◽  
Covalent Interactions

The coupling of cis-[PdCl2(CNXyl)2] (Xyl = 2,6-Me2C6H3) with 4-phenylthiazol-2-amine in molar ratio 2:3 at RT in CH2Cl2 leads to binuclear (diaminocarbene)PdII complex 3c. The complex was characterized by HRESI+-MS, 1H NMR spectroscopy, and its structure was elucidated by single-crystal XRD. Inspection of the XRD data for 3c and for three relevant earlier obtained thiazole/thiadiazole derived binuclear diaminocarbene complexes (3a EYOVIZ; 3b: EYOWAS; 3d: EYOVOF) suggests that the structures of all these species exhibit intra-/intermolecular bifurcated chalcogen bonding (BCB). The obtained data indicate the presence of intramolecular S•••Cl chalcogen bonds in all of the structures, whereas varying of substituent in the 4th and 5th positions of the thiazaheterocyclic fragment leads to changes of the intermolecular chalcogen bonding type, viz. S•••π in 3a,b, S•••S in 3c, and S•••O in 3d. At the same time, the change of heterocyclic system (from 1,3-thiazole to 1,3,4-thiadiazole) does not affect the pattern of non-covalent interactions. Presence of such intermolecular chalcogen bonding leads to the formation of one-dimensional (1D) polymeric chains (for 3a,b), dimeric associates (for 3c), or the fixation of an acetone molecule in the hollow between two diaminocarbene complexes (for 3d) in the solid state. The Hirshfeld surface analysis for the studied X-ray structures estimated the contributions of intermolecular chalcogen bonds in crystal packing of 3a–d: S•••π (3a: 2.4%; 3b: 2.4%), S•••S (3c: less 1%), S•••O (3d: less 1%). The additionally performed DFT calculations, followed by the topological analysis of the electron density distribution within the framework of Bader’s theory (AIM method), confirm the presence of intra-/intermolecular BCB S•••Cl/S•••S in dimer of 3c taken as a model system (solid state geometry). The AIM analysis demonstrates the presence of appropriate bond critical points for these interactions and defines their strength from 0.9 to 2.8 kcal/mol indicating their attractive nature.

scholarly journals Solid-State Structures and Photoluminescence of Lamellar Architectures of Cu(I) and Ag(I) Paddlewheel Clusters with Hydrogen-Bonded Polar Guests

Molecules ◽  
2021 ◽  
Vol 26 (21) ◽  
pp. 6731
Author(s):  
Haruki Inoue ◽  
Yuga Yamashita ◽  
Yoshiki Ozawa ◽  
Toshikazu Ono ◽  
Masaaki Abe
Keyword(s):  
Solid State ◽  
Diffuse Reflectance Spectroscopy ◽  
X Ray Diffraction ◽  
Uv Illumination ◽  
Near Ir ◽  
Carboxylic Groups ◽  
Dta Analysis ◽  
Non Covalent Interactions ◽  
Solid State Structures ◽  
Covalent Interactions

Two hexanuclear paddlewheel-like clusters appending six carboxylic-acid pendants have been isolated with the inclusion of polar solvent guests: [Cu6(Hmna)6]·7DMF (1·7DMF) and [Ag6(Hmna)6]·8DMSO (2·8DMSO), where H2mna = 2-mercaptonicotininc acid, DMF = N,N’-dimethylformamide, and DMSO = dimethyl sulfoxide. The solvated clusters, together with their fully desolvated forms 1 and 2, have been characterized by FTIR, UV–Vis diffuse reflectance spectroscopy, TG-DTA analysis, and DFT calculations. Crystal structures of two solvated clusters 1·7DMF and 2·8DMSO have been unambiguously determined by single-crystal X-ray diffraction analysis. Six carboxylic groups appended on the clusters trap solvent guests, DMF or DMSO, through H-bonds. As a result, alternately stacked lamellar architectures comprising of a paddlewheel cluster layer and H-bonded solvent layer are formed. Upon UV illumination (λex = 365 nm), the solvated hexasilver(I) cluster 2·8DMSO gives intense greenish-yellow photoluminescence in the solid state (λPL = 545 nm, ΦPL = 0.17 at 298 K), whereas the solvated hexacopper(I) cluster 1·7DMF displays PL in the near-IR region (λPL = 765 nm, ΦPL = 0.38 at 298 K). Upon complete desolvation, a substantial bleach in the PL intensity (ΦPL < 0.01) is observed. The desorption–sorption response was studied by the solid-state PL spectroscopy. Non-covalent interactions in the crystal including intermolecular H-bonds, CH···π interactions, and π···π stack were found to play decisive roles in the creation of the lamellar architectures, small-molecule trap-and-release behavior, and guest-induced luminescence enhancement.

scholarly journals Thermal solid-state Z/E isomerization of 2-alkylidene-4-oxothiazolidines: Effects of non-covalent interactions

2011 ◽  
Vol 76 (3) ◽  
pp. 317-328 ◽  
Author(s):  
Zdravko Dzambaski ◽  
Milovan Stojanovic ◽  
Marija Baranac-Stojanovic ◽  
Dragica Minic ◽  
Rade Markovic
Keyword(s):  
Solid State ◽  
1H Nmr Spectroscopy ◽  
Amorphous State ◽  
Intramolecular Hydrogen Bonding ◽  
Scanning Calorimetry ◽  
X Ray ◽  
Configurational Isomerization ◽  
Non Covalent Interactions ◽  
Intramolecular Hydrogen ◽  
Covalent Interactions

Configurational isomerization of stereo-defined 5-substituted and unsubstituted 2-alkylidene-4-oxothiazolidines 1 in the solid state, giving the Z/E mixtures in various ratios, was investigated by 1H-NMR spectroscopy, X-ray powder crystallography and differential scanning calorimetry (DSC). The Z/E composition can be rationalized in terms of non-covalent interactions, involving intermolecular and intramolecular hydrogen bonding and directional non-bonded 1,5-type S...O interactions. X-Ray powder crystallography, using selected crystalline (Z)-4- oxothiazolidine substrates, revealed transformation to the amorphous state during the irreversible Z ? E process. A correlation between previous results on the Z/E isomerization in solution and now in the solid state was established.

Synthesis, structural properties and reactivity of ruthenocene-based pincer Pd(ii) tetrahydroborate

2019 ◽  
Vol 48 (33) ◽  
pp. 12720-12729 ◽  
Author(s):  
Sergey V. Safronov ◽  
Evgenii I. Gutsul ◽  
Igor E. Golub ◽  
Fedor M. Dolgushin ◽  
Yulia V. Nelubina ◽  
...  
Keyword(s):  
Structural Properties ◽  
Crystal Packing ◽  
Non Covalent Interactions ◽  
Active Intermediates ◽  
Covalent Interactions ◽  
Bonded Complexes

Non-covalent interactions determine the structure, crystal packing and reactivity of isolated ruthenocene-based pincer Pd(ii) complexes. Bifurcate dihydrogen-bonded complexes are active intermediates of tetrahydroborate alcoholysis.

Second-order nonlinear optical properties of eight-membered centrosymmetric cyclic borasiloxanes

2019 ◽  
Vol 43 (27) ◽  
pp. 10948-10958
Author(s):  
Mohan Gopalakrishnan ◽  
Thamodharan Viswanathan ◽  
Ezhumalai David ◽  
Krishnan Thirumoorthy ◽  
Nattamai S. P. Bhuvanesh ◽  
...  
Keyword(s):  
Optical Properties ◽  
Silicon Atom ◽  
Nonlinear Optical ◽  
Crystal Packing ◽  
Second Order ◽  
Nonlinear Optical Properties ◽  
Strong Electron ◽  
Non Covalent Interactions ◽  
Electron Withdrawing Group ◽  
Covalent Interactions

SHG efficiencies of eight-membered centrosymmetric cyclic borasiloxanes arise form distorted silicon atom, strong electron withdrawing group and non-covalent interactions in crystal packing.

Heteroleptic Zn(II) 3,5-diiodosalicylates: Structures, luminescence and features of non-covalent interactions in solid state

Polyhedron ◽  
2020 ◽  
pp. 114895
Author(s):  
Mikhail A. Bondarenko ◽  
Marianna I. Rakhmanova ◽  
Pavel E. Plyusnin ◽  
Pavel A. Abramov ◽  
Alexander S. Novikov ◽  
...  
Keyword(s):  
Solid State ◽  
Non Covalent Interactions ◽  
Covalent Interactions

scholarly journals A variable-temperature X-ray diffraction and theoretical study of conformational polymorphism in a complex organic molecule (DTC)

RSC Advances ◽  
2018 ◽  
Vol 8 (67) ◽  
pp. 38445-38454 ◽  
Author(s):  
Andrea Gionda ◽  
Giovanni Macetti ◽  
Laura Loconte ◽  
Silvia Rizzato ◽  
Ahmed M. Orlando ◽  
...  
Keyword(s):  
Theoretical Study ◽  
Crystal Packing ◽  
Variable Temperature ◽  
Asymmetric Unit ◽  
X Ray Diffraction ◽  
X Ray ◽  
Complex Organic Molecule ◽  
Non Covalent Interactions ◽  
Complex Organic ◽  
Covalent Interactions

A small conformational change in the asymmetric unit has a significant effect on how non-covalent interactions determine (i) the crystal packing and (ii) the effect of T on the relative balance of electrostatics and dispersion–repulsions.

scholarly journals A rationally designed perfluorinated host for the extraction of PFOA from water utilising non-covalent interactions

2018 ◽  
Vol 42 (10) ◽  
pp. 7956-7968 ◽  
Author(s):  
Harrison Omorodion ◽  
Miguel Palenzuela ◽  
Manuel Ruether ◽  
Brendan Twamley ◽  
James A. Platts ◽  
...  
Keyword(s):  
Solid State ◽  
Nmr Spectroscopy ◽  
Perfluorooctanoic Acid ◽  
Multinuclear Nmr ◽  
Multinuclear Nmr Spectroscopy ◽  
Non Covalent Interactions ◽  
Covalent Interactions

Three hosts for the encapsulation of perfluorooctanoic acid have been synthesized. The host:guest complexes have been characterized by multinuclear NMR spectroscopy in solution and the solid state.

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