Regio‐ and Enantioselective Photodimerization within the Confined Space of a Homochiral Ruthenium/Palladium Heterometallic Coordination Cage

Abstract

Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: http://dx.

A Tris(3‐pyridyl)stannane as a Building Block for Heterobimetallic Coordination Polymers and Supramolecular Cages

“…[19] However,i ti si nteresting to note that the more closely related MeSi(3-Py) 3 ligand does not form this structure with CuI, insteadp roducing a2 D[ Cu 6 I 6 ]-cluster MOF. 11 Attempts to produce as imilara rrangementt ot he latter using the same solvothermal conditions as in the previous study only produced intractable mixtureso fp roducts,r egardless of stoichiometry.T hus it appeared fromt his initial study that simply changing the bridgehead group from MeSi(3-Py) 3 to PhSn(3-Py) 3 leads to marked differences in coordination character. [16] This can be ascribed to two factors:( i) the change in ligand bite resulting from the incorporation of al arger atom at the bridging positiona nd (ii)potentially also to the differing steric influence of the Ph-group of 1 compared to the Megroup of MeSi(3-Py) 3 .…”

“…Although the paramagnetic nature of [Co 5 (1) 6 (H 2 O) 6 (NCMe) 6 ] [BF 4 ] 10 hamperedi n-depth 1 HNMR spectroscopic studies, the 11 Ba nd 19 FNMR spectra in MeCN at room temperature support the retention of the cage structure in solution, with both showingt wo BF 4 À environments in the expected 1:4r atio, along with drastically downfield-shifted resonances for the en- Chem.E ur.J. 2019, 25,14003 -14009 www.chemeurj.org capsulated BF 4 À anions (e.g., d F = À112.8 (1 F), À145.6 ppm (4 F), Supporting Information, Figures S17 and 18).…”

“…Room-temperature 1 H, 11 B, and 19 FNMR spectra were recorded on aBruker 400 MHz Avance III HD Smart Probe spectrometer.V ariable temperature 1 Ha nd 19 FNMR spectra were recorded on aB ruker 500 MHz AvanceI II HD Smart Probe spectrometer or on a5 00 MHz Agilent DD2 spectrometer.2 D 1 Ha nd 19 FD OSY spectra were acquired on the Agilent spectrometer using the Dbppste (DOSY) bipolar pulse pair stimulated echo pulse sequence. Typically,3 2g radient levels ranging from 6t o5 5Gcm À1 and 16 transients were used.…”

“…[3] This metalloligand strategy for the construction of heterometallic supramolecular architectures has been successfully enacted for av ariety of mixed transition metals ystems, for example, Fe/Pd, [2,[4][5][6] Fe/Ru, [7] Fe/Co, [8,9] Co/ Mn [5] and Ru/Pd. [10,11] However,t he use of main group metalloligands to createmixed main group/transitionmetal heterometallic systems is rare.…”

Proton in a Confined Space: Structural Studies of H+⊂Crypt‐111 Iodide and Some Halogen‐Bonded Derivatives

“…[2] When molecules are restrained in ac age, az ero-dimensional (0 D) confined space, their motion is mostly restricted and intermoleculari nteractions can be amplified [3] or the half-life of fleeting and reactive species can be extended. [4] In ac age, binding characteristics [5] as well as reactivity [6] and catalysis [7] may gain strong improvements in rate, selectivity,a nd yields. Unique and useful results can thus be achieved in different fields such as materials fabrication by self-assembly, [8] structural characterization at the nanogram scale, [9] and assessment of the mechanism-of-action of new drugs.…”