scholarly journals Bond orders for intermolecular interactions in crystals: charge transfer, ionicity and the effect on intramolecular bonds

IUCrJ ◽  
2018 ◽  
Vol 5 (5) ◽  
pp. 635-646 ◽  
Author(s):  
Khidhir Alhameedi ◽  
Amir Karton ◽  
Dylan Jayatilaka ◽  
Sajesh P. Thomas
Keyword(s):  
Charge Transfer ◽  
Intermolecular Interactions ◽  
Covalent Bond ◽  
Halogen Bonding ◽  
Close Packing ◽  
Bond Orders ◽  
Binding Motifs ◽  
Bond Indices ◽  
Interaction Regions

The question of whether intermolecular interactions in crystals originate from localized atom...atom interactions or as a result of holistic molecule...molecule close packing is a matter of continuing debate. In this context, the newly introduced Roby–Gould bond indices are reported for intermolecular `σ-hole' interactions, such as halogen bonding and chalcogen bonding, and compared with those for hydrogen bonds. A series of 97 crystal systems exhibiting these interaction motifs obtained from the Cambridge Structural Database (CSD) has been analysed. In contrast with conventional bond-order estimations, the new method separately estimates the ionic and covalent bond indices for atom...atom and molecule...molecule bond orders, which shed light on the nature of these interactions. A consistent trend in charge transfer from halogen/chalcogen bond-acceptor to bond-donor groups has been found in these intermolecular interaction regionsviaHirshfeld atomic partitioning of the electron populations. These results, along with the `conservation of bond orders' tested in the interaction regions, establish the significant role of localized atom...atom interactions in the formation of these intermolecular binding motifs.

scholarly journals Supramolecular interactions in the solid state

IUCrJ ◽  
2015 ◽  
Vol 2 (6) ◽  
pp. 675-690 ◽  
Author(s):  
Giuseppe Resnati ◽  
Elena Boldyreva ◽  
Petra Bombicz ◽  
Masaki Kawano
Keyword(s):  
Solid State ◽  
Intermolecular Interactions ◽  
Historical Review ◽  
Covalent Bond ◽  
Halogen Bonding ◽  
Molecular Assembly ◽  
Supramolecular Interactions ◽  
Ambient Conditions ◽  
Chemical Research ◽  
Primary Means

In the last few decades, supramolecular chemistry has been at the forefront of chemical research, with the aim of understanding chemistry beyond the covalent bond. Since the long-range periodicity in crystals is a product of the directionally specific short-range intermolecular interactions that are responsible for molecular assembly, analysis of crystalline solids provides a primary means to investigate intermolecular interactions and recognition phenomena. This article discusses some areas of contemporary research involving supramolecular interactions in the solid state. The topics covered are: (1) an overview and historical review of halogen bonding; (2) exploring non-ambient conditions to investigate intermolecular interactions in crystals; (3) the role of intermolecular interactions in morphotropy, being the link between isostructurality and polymorphism; (4) strategic realisation of kinetic coordination polymers by exploiting multi-interactive linker molecules. The discussion touches upon many of the prerequisites for controlled preparation and characterization of crystalline materials.

Role of Charge Transfer in Halogen Bonding

2021 ◽  
Author(s):  
Brandon Inscoe ◽  
Hemali Rathnayake ◽  
Yirong Mo
Keyword(s):  
Charge Transfer ◽  
Halogen Bonding

scholarly journals On the role of charge transfer in halogen bonding

2017 ◽  
Vol 19 (1) ◽  
pp. 791-803 ◽  
Author(s):  
Jan Řezáč ◽  
Aurélien de la Lande
Keyword(s):  
Charge Transfer ◽  
Interaction Energy ◽  
Halogen Bonding

We have quantified the energetic contribution of charge transfer to halogen bonding to be about 10% of the interaction energy.

Dynamic adjustment of emission from both singlets and triplets: the role of excited state conformation relaxation and charge transfer in phenothiazine derivates

2021 ◽  
Author(s):  
Weidong Qiu ◽  
Xinyi Cai ◽  
Mengke Li ◽  
Liangying Wang ◽  
Yanmei He ◽  
...  
Keyword(s):  
Excited State ◽  
Charge Transfer ◽  
Intramolecular Charge Transfer ◽  
Dynamic Adjustment ◽  
Twisted Intramolecular Charge Transfer

Dynamic adjustment of emission behaviours by controlling the extent of twisted intramolecular charge transfer character in excited state.

scholarly journals Role of Chemistry and Crystal Structure on the Electronic Defect States in Cs-Based Halide Perovskites

Materials ◽  
2021 ◽  
Vol 14 (4) ◽  
pp. 1032
Author(s):  
Anirban Naskar ◽  
Rabi Khanal ◽  
Samrat Choudhury
Keyword(s):  
Crystal Structure ◽  
Density Functional ◽  
Covalent Bond ◽  
Density Functional Theory Calculations ◽  
Antisite Defect ◽  
Defect States ◽  
Functional Theory ◽  
Electronic Defect ◽  
Constituent Elements

The electronic structure of a series perovskites ABX3 (A = Cs; B = Ca, Sr, and Ba; X = F, Cl, Br, and I) in the presence and absence of antisite defect XB were systematically investigated based on density-functional-theory calculations. Both cubic and orthorhombic perovskites were considered. It was observed that for certain perovskite compositions and crystal structure, presence of antisite point defect leads to the formation of electronic defect state(s) within the band gap. We showed that both the type of electronic defect states and their individual energy level location within the bandgap can be predicted based on easily available intrinsic properties of the constituent elements, such as the bond-dissociation energy of the B–X and X–X bond, the X–X covalent bond length, and the atomic size of halide (X) as well as structural characteristic such as B–X–B bond angle. Overall, this work provides a science-based generic principle to design the electronic states within the band structure in Cs-based perovskites in presence of point defects such as antisite defect.

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