Stronger π···π Interaction Leads to a Smaller Thermal Expansion in Some Charge Transfer Complexes

Saraswatula, Viswanadha G.; Sharada, Durgam; Saha, Binoy K.

doi:10.1021/acs.cgd.7b01502

Cited by 42 publications

(42 citation statements)

References 36 publications

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“…5). This direction corresponds to a combination of the principal X 1 and X 2 axes, in contrast to the cases reported in literature (Saha et al, 2017;Saraswatula et al, 2018;Crawford et al, 2019), where the major expansion occurs along thestacking direction; the combination of interactions between the paddlewheel complexes and the strong coordination bonds in the distinct complexes strengthen the chain-like motifs inhibiting any expansion along the X 1 and X 2 axes.…”

Section: Thermal Expansioncontrasting

confidence: 65%

Extraordinary anisotropic thermal expansion in photosalient crystals

Yadava

Gallo

Bette

et al. 2020

IUCrJ

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Although a plethora of metal complexes have been characterized, those having multifunctional properties are very rare. This article reports three isotypical complexes, namely [Cu(benzoate)L 2], where L = 4-styrylpyridine (4spy) (1), 2′-fluoro-4-styrylpyridine (2F-4spy) (2) and 3′-fluoro-4-styrylpyridine (3F-4spy) (3), which show photosalient behavior (photoinduced crystal mobility) while they undergo [2+2] cycloaddition. These crystals also exhibit anisotropic thermal expansion when heated from room temperature to 200°C. The overall thermal expansion of the crystals is impressive, with the largest volumetric thermal expansion coefficients for 1, 2 and 3 of 241.8, 233.1 and 285.7 × 10−6 K−1, respectively, values that are comparable to only a handful of other reported materials known to undergo colossal thermal expansion. As a result of the expansion, their single crystals occasionally move by rolling. Altogether, these materials exhibit unusual and hitherto untapped solid-state properties.

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Section: Thermal Expansioncontrasting

confidence: 65%

Extraordinary anisotropic thermal expansion in photosalient crystals

Yadava

Gallo

Bette

et al. 2020

IUCrJ

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“…It is the special structure of 1,3-DITFB that leads to the formation of the 2D sheet and furthers the formation of the sandwiched-layer structure of the cocrystal. A similar structure can be found in the cocrystal formed between HMB and 1,2,4,5-tetracyanobenzene [33]. This cocrystal also has a layer structure.…”

Section: Noncovalent Interactions In the Crystal Structuresupporting

confidence: 71%

“…The HMB molecules form the corrugated layers via dispersion forces. In the corrugated HMB layer, two methyl groups of HMB along the crystallographic a axis are disordered, and the other four methyl groups form four A similar structure can be found in the cocrystal formed between HMB and 1,2,4,5-tetracyanobenzene [33]. This cocrystal also has a layer structure.…”

Section: Noncovalent Interactions In the Crystal Structurementioning

confidence: 57%

Unexpected Sandwiched-Layer Structure of the Cocrystal Formed by Hexamethylbenzene with 1,3-Diiodotetrafluorobenzene: A Combined Theoretical and Crystallographic Study

Zhang

Wang

2020

Crystals

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The cocrystal formed by hexamethylbenzene (HMB) with 1,3-diiodotetrafluorobenzene (1,3-DITFB) was first synthesized and found to have an unexpected sandwiched-layer structure with alternating HMB layers and 1,3-DITFB layers. To better understand the formation of this special structure, all the noncovalent interactions between these molecules in the gas phase and the cocrystal structure have been investigated in detail by using the dispersion-corrected density functional theory calculations. In the cocrystal structure, the theoretically predicted π···π stacking interactions between HMB and the 1,3-DITFB molecules in the gas phase can be clearly seen, whereas there are no π···π stacking interactions between HMB molecules or between 1,3-DITFB molecules. The attractive interactions between HMB molecules in the corrugated HMB layers originate mainly in the dispersion forces. The 1,3-DITFB molecules form a 2D sheet structure via relatively weak C–I···F halogen bonds. The theoretically predicted much stronger C–I···π halogen bonds between HMB and 1,3-DITFB molecules in the gas phase are not found in the cocrystal structure. We concluded that it is the special geometry of 1,3-DITFB that leads to the formation of the sandwiched-layer structure of the cocrystal.

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“…26 Nonetheless, Saraswatula et al demonstrate that increasing the strength of the aromatic interactions can decrease thermal expansion in a series of similar aromatic molecules. 27 Glipizide is probably one of the earlier examples demonstrating uniaxial negative thermal expansion (NTE), although steric hindrance appears to be the cause of the uniaxial contraction on heating. 28 NTE has been observed for co-crystals with 4-phenylazopyridine, which was ascribed to a rotational movement of the molecules and to the hydrogen bonds present in the co-crystals.…”

Section: Introductionmentioning

confidence: 99%

Uniaxial Negative Thermal Expansion in Polymorphic 2-Bromobenzophenone, Due to Aromatic Interactions?

Romanini

Rietveld

Négrier

et al. 2021

Crystal Growth & Design

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The structure of the metastable form II of 2-bromobenzophenone, obtained by crystallization from the melt, has been determined by powder X-ray diffraction. Form II has been solved in the centrosymmetric monoclinic space group P21/c with a = 8.4896(19) Å, b = 6.5438(8) Å, c = 20.253(1) Å; β = 104.452(6)° and Z = 4 (Z' = 1) at 200 K. Both form I and form II contain a multitude of aromatic interactions and the strength and direction of these interactions could only be interpreted with the support of the thermal expansion tensors. Both forms exhibit, unexpectedly, uniaxial negative thermal expansion, while hydrogen bonding does not play a significant role in either of these two structures. It appears to be the first time in the literature that uniaxial negative thermal expansion may be caused by aromatic interactions. Thermodynamic properties at normal and high pressure have been determined for the stable and metastable phases and a pressure-temperature phase diagram has been constructed. While the metastable form behaves monotropically with respect to the stable form under ambient conditions, the phase relationship becomes enantiotropic at high pressure, providing a clear example of phase behavior in which the densest form is not the most stable form under ambient conditions.

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Stronger π···π Interaction Leads to a Smaller Thermal Expansion in Some Charge Transfer Complexes

Cited by 42 publications

References 36 publications

Extraordinary anisotropic thermal expansion in photosalient crystals

Extraordinary anisotropic thermal expansion in photosalient crystals

Unexpected Sandwiched-Layer Structure of the Cocrystal Formed by Hexamethylbenzene with 1,3-Diiodotetrafluorobenzene: A Combined Theoretical and Crystallographic Study

Uniaxial Negative Thermal Expansion in Polymorphic 2-Bromobenzophenone, Due to Aromatic Interactions?

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