Aurophilicity‐Mediated Construction of Emissive Porous Molecular Crystals as Versatile Hosts for Liquid and Solid Guests

Abstract

The first examples of porousm olecular crystals that are assembled through Au···Au interactions of gold complex 1 are here reporteda long with their exchange properties with respect to their guestc omponents.S inglecrystal X-ray diffraction (XRD) analyses indicatet hat the crystal structure of 1/CH 2 Cl 2 ·pentane is based on cyclic hexamers of 1,w hich are formedt hrough six Au···Au interactions. The packingo ft hese cyclic hexamers affords ap orousa rchitecture, in which the one-dimensionalc hannel segmentc ontains CH 2 Cl 2 and pentane as guests. These guestsc an be ex-changed through operationally simple methods under retention of the host framework of 1,w hich furnished 1/guest complexes with 26 differentg uests.As ingle-crystal XRD analysiso f1/eicosane, which contains the long linear alkane eicosane (n-C 20 H 42 ), successfully provided its accurately modeled structurew ithin the porous material. These host-guest complexes show chromic luminescence with both blue-and redshifted emissions.M oreover,t his porouso rganometallic materialcan exhibit luminescentmechanochromism through release of guests.[a] Dr.Figure 10. Emission spectra of 1/CH 2 Cl 2 ·pentane(blue line)and 1 ground (green line). Inset shows aphotographo f1 ground recorded under UV light.Figure 9. a) Optimized triplet structure of 1/CH 2 Cl 2 ·pentane.b )Upper and c) lowerS OMO of the optimized triplet structure of 1/CH 2 Cl 2 ·pentane. Ad etailed description of the modeling and calculation conditionsisg iven in the Supporting Information.

Molecular gold strings: aurophilicity, luminescence and structure–property correlations

“…In a similar study, Ito and co-workers presented the formation of crystals comprising gold isocyanides as a versatile host system with guest-dependent luminescence. 202 In 2016, Ito and co-workers reported the synthesis of phenyl( phenylisocyanide)gold(I) (13a) and phenyl(3,5-dimethylphenylisocyanide)gold(I) (13b), which exhibit mechano triggered SCSC phase transformations and possess interesting optical and electronic properties. 23,[203][204][205] Complexes 13a and 13b were obtained as blue-and green-emitting single crystals respectively.…”

Molecular copper iodide clusters: a distinguishing family of mechanochromic luminescent compounds

“…The majority of the mechanochromic luminescent compounds are based on organic molecules, [12][13][14] in comparison with the metal-based compounds. 15 The latter demonstrated nonetheless a rich variety of mechanochromic properties, mainly based on Au [16][17][18][19][20][21][22][23][24][25][26][27][28][29] and Pt [30][31][32][33][34][35][36][37][38][39][40][41] complexes. Examples of Zn, [42][43][44][45][46][47][48][49] Al, 50,51 Ir [52][53][54][55][56][57][58][59][60][61]…”

Mechanically responsive luminescent films based on copper iodide clusters

“…Over the past decade, the reports on luminescent mechanochromic compounds have shown a great increase, mostly based on organic dyes. [17][18][19] The metal-based compounds [20][21][22] have also demonstrated a rich panel of mechanochromic properties involving mainly gold [23][24][25][26][27][28][29][30][31][32][33][34] and platinum [35][36][37][38][39][40][41][42][43][44][45][46] complexes. In general, the mechanochromism responsible for the mechanochromic properties is ascribed to reversible transitions of molecular conformations and/or intermolecular interactions between thermodynamically metastable and stable states.…”