Anisotropic Thermal Expansion as the Source of Macroscopic and Molecular Scale Motion in Phosphorescent Amphidynamic Crystals

Jin, Mingoo; Yamamoto, Sho; Seki, Tomohiro; Ito, Hajime; Garcı́a-Garibay, Miguel A.

doi:10.1002/ange.201909048

Cited by 49 publications

(8 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A second subgroup of rotors in Figure feature tri( p -fluorophenyl)phosphine endgroups as opposed to triphenylsilyl endgroups. , The phosphines in turn anchor digold rotators of the formula AuCC–( p -C 6 R 4 )–CCAu, with R 4 = H 4 ( 127 ), Me 4 ( 130 ), F 2 D 2 ( 128 - d 2 ), and F 4 ( 129 ). Outside of the MOF systems described below, these represent the only metal containing rotors studied in the Garcia-Garibay group, with one underlying goal being the modulation of phosphorescence emission.…”

Section: Systems From the Garcia-garibay Groupmentioning

confidence: 99%

“…Outside of the MOF systems described below, these represent the only metal containing rotors studied in the Garcia-Garibay group, with one underlying goal being the modulation of phosphorescence emission. All of these adducts can be crystallized in solvent-free forms. , Aurophilic interactions between neighboring molecules are evident (Au–Au 2.95–3.36 Å) and are clearly a factor in the packing motifs.…”

Section: Systems From the Garcia-garibay Groupmentioning

confidence: 99%

“…The interpretation of the dynamic behavior of the difluoro compound 128 - d 2 was complicated by a nonlinear Arrhenius plot . This was attributed to reversible expansion/compression of the distances between the axes, giving E a values of 3.3–6.7 kcal/mol.…”

Section: Systems From the Garcia-garibay Groupmentioning

confidence: 99%

“…The related disilicon and bis(triaryl phosphine) digold rotors in Figure ( 123 – 126 and 127 – 130 ) have been accessed as shown in Figure . ,, In the final step in the disilicon series, the diconjugate dibase of a HCC–( p -arylene)–CCH species is treated with an excess of Ph 3 SiCl. In the diphosphorus series, the electrophile is switched to Ar 3 PAuCl.…”

Section: Systems From the Garcia-garibay Groupmentioning

confidence: 99%

See 3 more Smart Citations

Gyroscopes and the Chemical Literature, 2002–2020: Approaches to a Nascent Family of Molecular Devices

Ehnbom

Gladysz

2021

Chem. Rev.

View full text Add to dashboard Cite

Research directed toward the goal of molecular gyroscopes since the coverage of a previous review (2002) is described. Such species are a subclass of molecular rotors, which are comprised of rotators and stators. Major categories include (1) systems in which a rotator is embedded in a cage-like stator reminiscent of mechanical toy gyroscopes and (2) molecules that have been engineered to crystallize with parallel rotators and voids or other features that enable the rotator to rotate in the solid state (amphidynamic crystals). Particular attention is given to structural data and strategies for the minimization of rotational barriers. Synthetic routes are also described. Some allied types of molecules and supramolecular assemblies are also treated.

show abstract

Section: Systems From the Garcia-garibay Groupmentioning

confidence: 99%

Section: Systems From the Garcia-garibay Groupmentioning

confidence: 99%

Section: Systems From the Garcia-garibay Groupmentioning

confidence: 99%

Section: Systems From the Garcia-garibay Groupmentioning

confidence: 99%

See 2 more Smart Citations

Gyroscopes and the Chemical Literature, 2002–2020: Approaches to a Nascent Family of Molecular Devices

Ehnbom

Gladysz

2021

Chem. Rev.

View full text Add to dashboard Cite

show abstract

“…The use of deuterated gears was envisioned as a tool to simplify the 2 H NMR spectrum by removing potential overlapping of aromatic signals from the two components of the stator. Our group’s experience with gold complexes inspired us to bond the naphthyl diphosphine 9 to 8 via an Au 1+ coordination bond . Compound 9 was chosen as the 2,7-naphthyl substitution pattern to place the two phosphine groups 8.07 Å apart, a close fit for the idealized bibenzimidazole stator.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Gearing Fidelity Achieved Through Macrocyclization of a Solvated Molecular Spur Gear

et al. 2021

Self Cite

View full text Add to dashboard Cite

Molecular spur gear dynamics with high gearing fidelity can be achieved through a careful selection of constituent molecular components that favorably position and maintain the two gears in a meshed configuration. Here, we report the synthesis of a new macrocyclic molecular spur gear with a bibenzimidazole stator combined with a second naphthyl bis-gold-phosphine gold complex stator to place two 3-fold symmetric 9,10-diethynyl triptycene cogs at the optimal distance of 8.1 Å for gearing. Micro electron diffraction (μED) analysis confirmed the formation of the macrocyclic structure and the proper alignment of the triptycene cogs. Gearing dynamics in solution are predicted to be extremely fast and, in fact, were too fast to be observed with variable-temperature 1H NMR using CD2Cl2 as the solvent. A combination of molecular dynamics and metadynamics simulations predict that the barriers for gearing and slippage are ca. 4 kcal mol–1 and ca. 9 kcal mol–1, respectively. This system is characterized by enhanced gearing fidelity compared to the acyclic analog. This is achieved by rigidification of the structure, locking the two triptycenes in the preferred gearing distance and orientation.

show abstract

Molecular Spring‐like Triple‐Helix Coordination Polymers as Dual‐Stress and Thermally Responsive Crystalline Metal–Organic Materials

Mei

et al. 2020

Angewandte Chemie

View full text Add to dashboard Cite

Elastic metal–organic materials (MOMs) capable of multiple stimuli‐responsiveness based on dual‐stress and thermally responsive triple‐helix coordination polymers are presented. The strong metal‐coordination linkage and the flexibility of organic linkers in these MOMs, rather than the 4 Å stacking interactions observed in organic crystals, causes the helical chain to act like a molecular spring and thus accounts for their macroscopic elasticity. The thermosalient effect of elastic MOMs is reported for the first time. Crystal structure analyses at different temperatures reveal that this thermoresponsiveness is achieved by adaptive regulation of the triple‐helix chains by fine‐tuning the opening angle of flexible V‐shaped organic linkers and rotation of its lateral conjugated groups to resist possible expansion, thus demonstrating the vital role of adaptive reorganization of triple‐helix metal–organic chains as a molecular spring‐like motif in crystal jumping.

show abstract

Anisotropic Thermal Expansion as the Source of Macroscopic and Molecular Scale Motion in Phosphorescent Amphidynamic Crystals

Cited by 49 publications

References 55 publications

Gyroscopes and the Chemical Literature, 2002–2020: Approaches to a Nascent Family of Molecular Devices

Gyroscopes and the Chemical Literature, 2002–2020: Approaches to a Nascent Family of Molecular Devices

Enhanced Gearing Fidelity Achieved Through Macrocyclization of a Solvated Molecular Spur Gear

Molecular Spring‐like Triple‐Helix Coordination Polymers as Dual‐Stress and Thermally Responsive Crystalline Metal–Organic Materials

Contact Info

Product

Resources

About