Inorganic topochemistry. Vapor-induced solid state transformations of luminescent, three-coordinate gold(<scp>i</scp>) complexes

Lim, Sang Ho; Olmstead, Marilyn M.; Balch, Alan L.

doi:10.1039/c2sc20820b

Cited by 89 publications

(88 citation statements)

References 51 publications

(55 reference statements)

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“…19 As previously reported, recrystallization of this white powder produced Au 2 (µ-dppe) 2 I 2 with two, three-coordinate gold centers and a variable spacing between these gold centers and Au 2 (µ-dppe) 2 (µ−I) 2 with two, four-coordinate gold centers. 19 Attempts to oxidize "Au(dppe)I" with diiodine produced only colorless Au 2 (µ-dppe)I 2 in 77 % yield.…”

Section: Synthesis and Crystal Growthmentioning

confidence: 73%

“…For example, the dimers Au 2 (µ-dppe) 2 Br 2 and Au 2 (µ-dppe) 2 I 2 consist of two, three-coordinate P 2 AuX units. 18,19 Remarkably, the spacing between these three-coordinate, planar gold centers is variable and can range from ~3.2 Å to ~3.8 Å. 18,19 Thus, these molecules resemble molecular accordions.…”

Section: Introductionmentioning

confidence: 98%

“…18,19 Remarkably, the spacing between these three-coordinate, planar gold centers is variable and can range from ~3.2 Å to ~3.8 Å. 18,19 Thus, these molecules resemble molecular accordions. They are luminescent with their emission depending upon the Au•••Au separation.…”

Section: Introductionmentioning

confidence: 98%

“…When that spacing is less than 3.5 Å, the dimers have a green emission, but when the spacing is greater than 3.5 Å, a red emission is observed. 18,19 Our attempts to make the hypothetical molecular accordion "Au 2 (µ-dcpe) 2 X 2 " (where dcpe is 1,2-bis(dicyclohexylphosphino)ethane and X can be Cl, Br, or I), in which the phenyl groups were replaced with cyclohexyl substituents that could not contribute to the luminescence, resulted exclusively in the formation of the two-coordinate complexes, Au 2 (µ-dcpe)X 2 .…”

Section: Introductionmentioning

confidence: 99%

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Steric effects and aurophilic interactions in crystals of Au2(μ-1,2-bis(diphenylphosphino)ethane)X2 and Au2(μ-1,2-bis(dicyclohexylphosphino)ethane)X2 (X = Cl, Br, I)

et al. 2016

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Steric Effects and Aurophilic Interactions in Crystals of Au 2 (μ-1,2-bis(diphenylphosphino)ethane)X 2 and Au 2 (μ-1,2-bis(dicyclohexylphosphino)ethane)X 2 (X = Cl, Br, I), Polyhedron (2016), doi: http://dx. Abstract Crystalsin the isostructural series Au 2 (µ-dppe)X 2 (dppe is 1,2-bis(diphenylphosphino)ethane, X = Cl, Br, I) form centrosymmetric, dimeric structures with two short Au … Au contacts between the component molecules. We found no evidence for a second polymorph for any member of the Au 2 (µ-dppe)X 2 series, although two polymorphs were observed previously for the related Au 2 (Ph 2 As(CH 2 ) 2 AsPh 2 )X 2 series. Crystals of Au 2 (µ-dcpe)X 2 (where dcpe is 1,2-bis(dicyclohexylphosphino)ethane) show structures that differ appreciably from those of Au 2 (µ-dppe)X 2 . The bulky cyclohexyl substituents appear to be playing a major role eliminating the formation of polymeric or dimeric structures. Au 2 (µ-dcpe)Cl 2 has a monomeric structure without aurophilic interactions. In contrast, Au 2 (µ-dcpe)Br 2 and Au 2 (µ-dcpe)I 2 have similar structures with intramolecular aurophilic interactions. Au 2 (µ-dcpe)I 2 displays a form of aggregation-induced emission. It displays a red-pink luminescence in crystalline form but is non-emissive in solution.3

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Section: Synthesis and Crystal Growthmentioning

confidence: 73%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

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Steric effects and aurophilic interactions in crystals of Au2(μ-1,2-bis(diphenylphosphino)ethane)X2 and Au2(μ-1,2-bis(dicyclohexylphosphino)ethane)X2 (X = Cl, Br, I)

et al. 2016

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“…These color changes are caused by the mechano‐induced crystalline structural changes in the materials that alter the intermolecular interaction patterns. Most of the reported crystalline mechanochromic luminescent materials show crystal‐to‐amorphous phase transitions (approximately 70 %) . This is because the mechanical grinding or shearing is noncoherent and exerts random stimulation on the solid, which degrades the integrity of the materials.…”

Section: Introductionmentioning

confidence: 99%

Detailed Investigation of the Structural, Thermal, and Electronic Properties of Gold Isocyanide Complexes with Mechano‐Triggered Single‐Crystal‐to‐Single‐Crystal Phase Transitions

Seki

Sakurada

Muromoto

et al. 2016

Chemistry A European J

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Mechano-induced phase transitions in organic crystalline materials that alter their properties have received much attention. However, most mechano-responsive molecular crystals exhibit crystal to amorphous phase transitions on mechanical stimulation, and the intermolecular interaction patterns in the daughter phase are difficult to characterize. We investigated phenyl(phenylisocyanide)gold(I) (1) and phenyl(3,5-dimethylphenylisocyanide)gold(I) (2) complexes that exhibit a mechanotriggered single crystal to single crystal phase transition. Previous reports of 1 and 2 focused on relationships between the crystalline structures and photoluminescence properties; in this work we have focused on other aspects. The face index measurements of 1 and 2 before and after the mechano-induced phase transitions indicate they undergo non-epitaxial phase transitions without a rigorous orientational relationship between the mother and daughter phases. Differential scanning calorimetry analyses revealed the phase transition of 1 to be enthalpically driven by the formation of new aurophilic interactions. In contrast, the phase transition of 2 is entropically driven, with an empty void in the mother phase, not present in the daughter phase. Scanning electron microscopy observation showed that the degree of the charging effect of both 1 and 2 was changed by the phase transitions, suggesting that the formation of the aurophilic interactions affords more effective conductive pathways. Moreover, flashphotolysis time resolved microwave conductivity measurements revealed that 1 increased in conductivity after the phase change, whereas the conductivity of 2 decreased. These contrasting results were explained by the different patterns in the aurophilic interactions. Finally, an intriguing disappearing polymorphism of 2 is reported, in which a polymorph form could not be obtained again after some period of time even with repeated trials. The present studies provide us with a variety of hitherto unknown insights into mechano-responsive molecular crystals, which help us understand the phase transition behaviors upon mechanical stimulation and establish rational design principles.

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Two‐Component Molecular Materials of 2,5‐Diphenyloxazole Exhibiting Tunable Ultraviolet/Blue Polarized Emission, Pump‐enhanced Luminescence, and Mechanochromic Response

Yan

Yang

Meng

et al. 2013

Adv Funct Materials

197

144

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The development of π‐conjugated molecular systems with high‐efficiency generation of UV and blue light plays an important role in the fields of light‐emitting diodes, fluorescent imaging, and information storage. Herein, supramolecular construction of solid‐state UV/blue luminescent materials are assembled using 2,5‐diphenyloxazole (DPO) with four typical co‐assembled building blocks (1,4‐diiodotetrafluorobenzene, 4‐bromotetrafluorobenzene carboxylic acid, pentafluorophenol, and octafluoronaphthalene). Compared with the pristine DPO sample, the as‐prepared two‐component molecular materials feature ease of crystallization, high crystallinity, enhanced thermal stability and tunable luminescence properties (such as emissive wavelength, color, fluorescence lifetime, and photoluminescence quantum yield) as well as multicolor polarized emission in the UV/blue region. Moreover, pump‐enhanced luminescence and reversible mechanochromic fluorescence (MCF) properties can also be obtained for these molecular solids, which are absent for the pristine DPO sample. Therefore, this work provides a procedure for the facile self‐assembly of ordered two‐component molecular materials with tunable UV/blue luminescence properties, which have potential application in the areas of light‐emitting displays, polarized emission, frequency doubling, and luminescent sensors.

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Inorganic topochemistry. Vapor-induced solid state transformations of luminescent, three-coordinate gold(i) complexes

Cited by 89 publications

References 51 publications

Steric effects and aurophilic interactions in crystals of Au2(μ-1,2-bis(diphenylphosphino)ethane)X2 and Au2(μ-1,2-bis(dicyclohexylphosphino)ethane)X2 (X = Cl, Br, I)

Steric effects and aurophilic interactions in crystals of Au2(μ-1,2-bis(diphenylphosphino)ethane)X2 and Au2(μ-1,2-bis(dicyclohexylphosphino)ethane)X2 (X = Cl, Br, I)

Detailed Investigation of the Structural, Thermal, and Electronic Properties of Gold Isocyanide Complexes with Mechano‐Triggered Single‐Crystal‐to‐Single‐Crystal Phase Transitions

Two‐Component Molecular Materials of 2,5‐Diphenyloxazole Exhibiting Tunable Ultraviolet/Blue Polarized Emission, Pump‐enhanced Luminescence, and Mechanochromic Response

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