The effect of temperature on interhalogen interactions in a series of isostructural organic systems

Saraswatula, Viswanadha G.; Saha, Binoy K.

doi:10.1039/c3nj01395b

Cited by 45 publications

(44 citation statements)

References 51 publications

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“…This situation allows a direct comparison of energies in different X•••X pairs by means of theoretical methods. However, while Cl/Br or Br/I isostructural pairs are common, the 'triple' series are very rare [12,13] especially in coordination chemistry [14,15].…”

Section: Introductionmentioning

confidence: 99%

Halogen Bonding in Isostructural Co(II) Complexes with 2-Halopyridines

et al. 2020

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Section: Introductionmentioning

confidence: 99%

Halogen Bonding in Isostructural Co(II) Complexes with 2-Halopyridines

et al. 2020

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“…The electrostatic nature of type II halogen bonding (Metrangolo & Resnati, 2014;Mukherjee & Desiraju, 2014) means that crystal structures containing these interactions are more responsive to temperature changes (thermosalient effects). Saraswatula & Saha (2014) reported that thermal expansion of inter-halogen distances is higher for lower halogens (chlorine) and a decrease in expansion was observed with an increase in the halogen-bond strength. So the behaviour of heavier halogen atom-containing species is different from that of the lower halogens.…”

Section: Compoundmentioning

confidence: 99%

Thermomechanical effect in molecular crystals: the role of halogen-bonding interactions

Mittapalli

Perumalla

Nanubolu

et al. 2017

IUCrJ

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The design and synthesis of mechanically responsive materials is interesting because they are potential candidates to convert thermal energy into mechanical work. Reported in this paper are thermosalient effects in a series of halogen derivatives of salinazids. The chloro derivative, with higher electronegativity and a weaker inter-halogen bond strength (ClÁ Á ÁCl) exhibits an excellent thermal response, whereas the response is weaker in the iodo derivative with stronger IÁ Á ÁI halogen bonding. 3,5-Dichlorosalinazid (Compound-A) exists in three polymorphic forms, two room-temperature polymorphs (Forms I and II) and one high-temperature modification (Form III). The transformation of Form I to Form III upon heating at 328-333 K is a reversible thermosalient transition, whereas the transformation of Form II to Form III is irreversible and nonthermosalient. 3,5-Dibromo-(Compound-B) and 3-bromo-5-chloro-(Compound-C) salinazid are both dimorphic: the Form I to Form II transition in Compound-B is irreversible, whereas Compound-C shows a reversible thermosalient effect (362-365 K). In the case of 3,5-diiodosalinazid (Compound-D) and 3,5-difluorosalinazid (Compound-E), no phase transitions or thermal effects were observed. The thermosalient behaviour of these halosalinazid molecular crystals is understood from the anisotropy in the cell parameters (an increase in the a axis and a decrease in the b and c axes upon heating) and the sudden release of accumulated strain during the phase transition. The dihalogen salinazid derivatives (chlorine to iodine) show a decrease in thermal effects with an increase in halogen-bond strength. Interestingly, Compound-B shows solid-state photochromism in its polymorphs along with the thermosalient effect, wherein Form I is cyan and Form II is light orange.

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“…Previously we had shown that thermal expansions of solvates are ∼25% more than that of guest-free forms in a series of interhalogen interaction mediated organic lattices. 63 Relatively small thermal expansion in the channel structures, especially in the case of BrPOT•DCM−channel system, could be due to lower guest content of the channels. In spite of having solid guest molecule in the cavity, the corresponding isostructural channel structure of BrPOT• HMB−channel (α v = 198(7) MK −1 ) exhibits stronger thermal expansion than that of BrPOT•DCM−channel but smaller thermal expansion than the BrPOT• HMB−cage-II (α v = 225(7) MK −1 ) structure.…”

Section: Interaction (Table S4) C−h• • • N and C−h• • • O Interactiomentioning

confidence: 99%

Network and guest dependent thermal stability and thermal expansion in a trigonal host

et al. 2014

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Thermal stability and thermal expansion of bromo trimer synthon mediated hexagonal inclusion compounds of 2,4,6-tris(4-bromophenoxy)-1,3,5-triazine (BrPOT) with dichloromethane (DCM), tetrahydrofuran (THF) and hexamethyl benzene (HMB) and also the guest-free form of BrPOT are reported. Each of these three guests produced two concomitant inclusion compounds with BrPOT. The thermal stability of the solvate lattice increases with decreasing cavity size. The channel network of the DCM inclusion compound is stable only for a few seconds at room temperature outside the mother liquor, whereas the cage network of the DCM solvate is stable for months under similar conditions. Thermal expansions of the lattices depend upon the network, guest content as well as the type of guest molecules. The guest-free form exhibits the least thermal expansion in this series of systems.

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The effect of temperature on interhalogen interactions in a series of isostructural organic systems

Abstract: The order of thermal expansion of the interhalogen interactions is I⋯I < Br⋯Br < Cl⋯Cl, indicating that the order of interhalogen interaction strength is I⋯I > Br⋯Br > Cl⋯Cl.

Cited by 45 publications

References 51 publications

Halogen Bonding in Isostructural Co(II) Complexes with 2-Halopyridines

Halogen Bonding in Isostructural Co(II) Complexes with 2-Halopyridines

Thermomechanical effect in molecular crystals: the role of halogen-bonding interactions

Network and guest dependent thermal stability and thermal expansion in a trigonal host

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