Compressed Corannulene in a Molecular Cage Schmidt, Bernd M.; Osuga, Takafumi; Sawada, Tomohisa ...
Angewandte Chemie (International ed.),
January 22, 2016, Letnik:
55, Številka:
4
Journal Article
Recenzirano
Self‐assembled coordination cages can be employed as a molecular press, where the bowl‐shaped guest corannulene (C20H10) is significantly flattened upon inclusion within the hydrophobic cavity. This ...is demonstrated by the pairwise inclusion of corannulene with naphthalene diimide as well as by the dimer inclusion of bromocorannulene inside the box‐like host. The compressed corannulene structures are unambiguously revealed by single‐crystal X‐ray analysis.
Molecular compressor: Self‐assembled coordination cages can compress the bowl‐shaped guest corannulene when encapsulated in a pillared cage. Unsubstituted corannulene was pairwise included together with naphthalene diimide, while bromocorannulene formed a defined homodimer to be accommodated.
Ion nanowire: Electron transport through discrete gold‐ion arrays within coordination cages was directly measured between Au nanogap electrodes (see picture) using STM. Precise calibration of the ...electron transport distance demonstrates that Au‐ion arrays exhibit good conductance and only moderate loss with increasing transport length.
A tray‐shaped PdII3AuI3 complex (1) is prepared from 3,5‐bis(3‐pyridyl)pyrazole by means of tricyclization with AuI followed by PdII clipping. Tray 1 is an efficient scaffold for the modular assembly ...of 3×n AuI clusters. Treatment of 1 with the AuI3 tricyclic guest 2 in H2O/CH3CN (7:3) or H2O results in the selective formation of a 3×2 cluster (1⋅2) or a 3×3 cluster (1⋅2⋅1), respectively. Upon subsequent addition of AgI ions, these complexes are converted to an unprecedented Au3–Au3–Ag–Au3–Au3 metal ion cluster.
Pile up gold: A PdII3AuI3 shallow concave complex was prepared by connecting peripheral pyridyl groups of a planar AuI3 complex with each other through PdII coordination. The tray‐shaped host accommodated the AuI3 planes to form three‐dimensional AuI arrays. The number of AuI3 stacks (n) was systematically tuned by the solvent conditions and the addition of AgI ions.
A tray‐shaped PdII3AuI3 complex (1) is prepared from 3,5‐bis(3‐pyridyl)pyrazole by means of tricyclization with AuI followed by PdII clipping. Tray 1 is an efficient scaffold for the modular assembly ...of 3×n AuI clusters. Treatment of 1 with the AuI3 tricyclic guest 2 in H2O/CH3CN (7:3) or H2O results in the selective formation of a 3×2 cluster (1⋅2) or a 3×3 cluster (1⋅2⋅1), respectively. Upon subsequent addition of AgI ions, these complexes are converted to an unprecedented Au3–Au3–Ag–Au3–Au3 metal ion cluster.
Gold anhäufen: Ein flacher, konkaver PdII3AuI3‐Komplex wurde durch die PdII‐vermittelte Verbindung der peripheren Pyridylgruppen eines planaren AuI3‐Komplexes erzeugt. Der schalenförmige Wirt nimmt die flachen AuI3‐Gäste auf und bildet dreidimensionale AuI‐Anordnungen. Die Anzahl der AuI3‐Stapel (n) wurde durch die Änderung des Lösungsmittels und durch die Zugabe von AgI‐Ionen systematisch verändert.
Aromatic stacks formed through self-assembly are promising building blocks for the construction of molecular electronic devices with adjustable electronic functions, in which noncovalently bound ...π-stacks act as replaceable modular components. Here we describe the electron-transport properties of single-molecule aromatic stacks aligned in a self-assembled cage, using scanning probe microscopic and break junction methods. Same and different modular aromatic pairs are noncovalently bound and stacked within the molecular cage holder, which leads to diverse electronic functions. The insertion of same pairs induces high electronic conductivity (10–3–10–2 G 0, G 0 = 2e 2/h), while different pairs develop additional electronic rectification properties. The rectification ratio was, respectively, estimated to be 1.4–2 and >10 in current–voltage characteristics and molecular orientation-dependent conductance measurements at a fixed bias voltage. Theoretical calculations demonstrate that this rectification behavior originates from the distinct stacking order of the internal aromatic components against the electron-transport direction and the corresponding lowest unoccupied molecular orbital conduction channels localized on one side of the molecular junctions.
Three-dimensional m × n arrays of metal ion clusters can be assembled as aromatic stacks of planar polynuclear metal complexes within columnar coordination cages. The polynuclear complexes and cage ...height program the final array structures of the metal ion clusters. Cyclic trinuclear Au(I) complexes (m = 3) assembled into trigonal prismatic arrays (n = 1−3) within the cages and the array structures were clearly shown by X-ray crystallographic analysis. A silver-sandwiched hetero-Au3−Ag−Au3 cluster was also prepared by treating a hexanuclear Au3−Au3 cluster with Ag(I) ion.
Abstract
A tray‐shaped Pd
II
3
Au
I
3
complex (
1
) is prepared from 3,5‐bis(3‐pyridyl)pyrazole by means of tricyclization with Au
I
followed by Pd
II
clipping. Tray
1
is an efficient scaffold for ...the modular assembly of 3×n Au
I
clusters. Treatment of
1
with the Au
I
3
tricyclic guest
2
in H
2
O/CH
3
CN (7:3) or H
2
O results in the selective formation of a 3×2 cluster (
1
⋅
2
) or a 3×3 cluster (
1
⋅
2
⋅
1
), respectively. Upon subsequent addition of Ag
I
ions, these complexes are converted to an unprecedented Au
3
–Au
3
–Ag–Au
3
–Au
3
metal ion cluster.
