A 116‐Nuclear Metallosupramolecular Cage‐of‐Cage Showing Multistep Single‐Crystal‐to‐Single‐Crystal Transformation

Abstract

Here au nique single-crystal-to-single-crystal (SCSC) transformationo fa116-nuclear Au I 72 Cd II 40 Na I 4 cageof-cage( 2 CdNa )i sreported, which was created from at rigold(I) metalloligand with d-penicillamine by way of a9 -nuclear Au I 6 Cd II 3 cage (1). Cage-of-cage 2 CdNa is composedo f1 2 cages of 1 that are linked by 4C d 2 + and 4N a + ions, with its surface being covered by 12 NO 3 À ions to form ad iscrete, spherical molecule with ad iameter ca. 4.7 nm. In crystal 2 CdNa ,t he cage-of-cage molecules are packed in ac ubic lattice with ah uge cell volumeo fc a. 4.5 10 5 3 , so as to have large interstices with diameters of more than 3nm. Upon soakingc rystals 2 CdNa in aqueous Cu(NO 3 ) 2 ,a ll Cd 2 + and Na + were quicklye xchanged by Cu 2 + to producea na nalogous Au I 72 Cu II 44 cage-of-cage (2 Cu )i naSCSC manner.P rolonged soakingl ed to the SCSC transformation to anothers upramolecular structure (2' Cu )c onsisting of 152-nuclear Au I 72 Cu II 80 cage-of-cages that are alternately H-bonded with the Au I 72 Cu II 44 cage-of-cages. 2' Cu showed the accommodationo f MoO 4 2À and the conversion of MoO 4 2À to b-Mo 8 O 26 4À in the crystal, with retention of single-crystallinity. Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.org/10.1002/chem.201904275.Scheme1.Synthetic routes to 1 and 2 CdNa .C olor codes: red,A u; cream, Cd; purple, Na.

Single‐Crystal‐to‐Single‐Crystal Installation of Ln4(OH)4 Cubanes in an Anionic Metallosupramolecular Framework

“…In contrast to the development of PSMs in infinite porous materials, PSMs of crystalline metallosupramolecular compounds consisting of discrete molecules or ions are much less explored, mainly due to the inherent weakness of their frameworks, which consist of noncovalent interactions . The limited examples involve i) the exchange of counterions or solvents, ii) the condensation of guest molecules or ions, and iii) the coordination of guest molecules or ions to host metal centers …”

A mesoporous ionic solid with 272 AuI6AgI3CuII3 complex cations in a super huge crystal lattice

“…Synthesis, characterization and crystal structure of I 0 As a continuation of our recent work on the creation of multinuclear coordination compounds based on the trigold(I) metalloligand with a mixture of hydrophobic 1,1,1-tris(diphenylphosphinomethyl)ethane (tdme) and hydrophilic D-penicillamine (D-H 2 pen), [Au 3 (tdme)(D-Hpen) 3 ] (D-H 3 L Au3 ), [36][37][38] D-H 3 L Au3 was treated with 1.5 equiv. of silver(I) triuoroacetate in MeOH/ CH 3 CN at 0 C. This treatment yielded a colourless solution, from which colourless stick crystals were isolated upon addition of aqueous sodium nitrate.…”

Zn(II)-to-Cu(II) Transmetalation in an Amide Functionalized Complex and Catalytic Applications in Styrene Oxidation and Nitroaldol Coupling

“…It thus provides a common and convenient method for preparing various organo-transition metal complexes, which are otherwise difficult to synthesize via direct metal-ligand self-assembly. Such phenomenon is well documented and has expanded to other types of materials [4][5][6][7][8][9][10][11]. The process usually proceeds through either "direct exchange", where the incoming metal does not alter the topology of the frameworks or through "disruptive exchange" in which the geometry of the transmetalation complex differs from the original structure as a result of the metal exchange.…”