Self-Assembly of Gold(I) Rings and Reversible Formation of Organometallic [2]Catenanes

Dual Luminescent Tetranuclear Organogold(I) Macrocycles of 5,5′-Diethynyl-2,2′-bipyridine and Their Efficient Sensitization of Yb(III) Luminescence

“…The bond distances of Au−P (2.265 (7) 25 The unit cell of complex 1·3CH 2 Cl 2 consists of three 2:4:2 rings of complex 1 and nine DCM solvent molecules. 3,5,11 The bridging dppm adopts a cis-conformation, with the angles Au1− P1···Au2−P2 = 12.7°, Au3−P3···Au4−P4 = 19.7°, and Au5− P5···Au6−P6 = 27.9°, as in other gold(I) complexes with bridging cis-dppm ligands. 4,10,45−47 The two Au···Au units in the macrocycle with boat conformation containing Au1, Au2, Au3, and Au4 are twisted against each other with a separation angle of 24.7°, while the dihedral angle between the two dialkyne ligands is 8.8°; it can therefore avoid the larger repulsion resulting from face-to-face arrangement.…”

“…So structures containing simple 1:2:1 macrocycles as shown in Scheme 1b and c are not possible for complexes 1−6 because of the small P···P distances, although a lot of simple 1:2:1 macrocycles have been reported for the flexible dialkyne ligands. 1,5,7,8,11,12 Even though, in some cases, such 1:2:1 macrocycles can be formed, the ring strain would be too great. Fourth, the HRMS results also support Finally, though the longest fore-andaft distance in the macrocycle of complex 2 is 21.895 Å for C47···C47A, the lateral intramolecular Au1···Au2 distance is only 5.963 Å, so the cavity of the macrocycle is not large enough to allow catenation, to say nothing of complex 1.…”

Structural and Photophysical Properties of (Phosphane)gold(I)‐Decorated 4,4′‐Diethynyl‐2,2′‐bipyridine Ligands

“…[3,[9][10][11] By combining phosphine and alkyne metal-binding domains at a gold(I) centre, one gains significant scope for the design of macromolecules: [12] rigid-rod P-Au-C≡C-domains and a wide range of readily accessible mono-, bi-and polydentate phosphine ligands containing sp 3 hybridized P atoms combine with a tendency for gold atoms to aggregate (so-called 'aurophilicity'). [13][14][15]16] Of the 215 compounds in the CSD (CSD v 5.3 with May 2009 updates, Conquest v. 1.11) [17] possessing R 3 PAuC≡C units, only 19 [9,[18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] exhibit intermolecular aurophilic interactions resulting in onedimensional Au...Au bonded polymers. Of particular relevance to our work is the trigold derivative ( n Bu 3 PAuC≡CCH 2 OCH 2 ) 3 CCH 2 Otpy (tpy = 2,2';6',2"-terpyridine) which forms one-dimensional chains with an oriented assembly in the solid state in which all the tpy units point in the same direction.…”

Gold catenanes

“…There are several cases in which the hinge group X forms a multiple atom bridge and the cavity becomes too large (Scheme 9). However, there are also cases in which there is a single atom bridge, when X]O, S, C]O or C]NR, when catenation is not observed [63,64,67,71]. In these cases, one of the C 6 H 4 rings is close to being coplanar with the CXC plane in order to maximize pconjugation and the resulting steric effect blocks catenation (Fig.…”

“…The chiral hinge group C(Me)CH 2 CMe 2 similarly causes the C 6 H 3 group to lie in the plane of the CXC unit and prevents catenation (Fig. 6c) [63].…”