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A new TPE based low molecular weight gelator (LMWG) which displays both AIE and MCIE phenomena in gel state has been synthesized. LMWG self-assembles to form 1D nanofibers which undergo morphology transformation to coordination polymer gel (CPG) nanotubes upon metal ion coordination. CPG shows enhanced mechanical stability along with tunable emission properties.

The first example of a homometallic neutral zirconaborane, [(Cp 2 Zr) 2 B 5 H 11 ], 1, has been prepared through the thermolysis of [Cp 2 Zr(BH 4 ) 2 ], generated from the fast metathesis reaction of [Cp 2 ZrCl 2 ] and LiBH 4 ·thf with BH 3 ·thf. The solid-state structure of 1 shows an open geometry with a planar B 3 ring. The bonding between the Zr center and the central B 3 ring was studied computationally by DFT methods, and based on the combined experimental and computational results compound 1 can be defined as a metal-stabilized arachno-B 3 H 9 . Further, in an attempt to synthesize a hybrid analogue of 1 by introducing two electron fragments into arachno-[(Cp 2 Zr)(Cp*Ir)B 4 H 10 ], 2, we have performed the reaction of 2 with [Ru 3 (CO) 12 ]. However, the reaction led to the formation of a hybrid metallaborane, [(Cp*Ir){Ru 3 (CO) 8 }B 4 H 10 ], 3.

A high-yielding synthetic route for the preparation of group 9 metallaboratrane complexes [Cp*MBH(L)2], 1 and 2 (1, M=Rh, 2, M=Ir; L=C7H4NS2) has been developed using [{Cp*MCl2}2] as precursor. This method also permitted the synthesis of an Rh-N,S-heterocyclic carbene complex, [(Cp*Rh)(L2)(1-benzothiazol-2-ylidene)] (3; L=C7H4NS2) in good yield. The reaction of compound 3 with neutral borane reagents led to the isolation of a novel borataallyl complex [Cp*Rh(L)2B{CH2C(CO2Me)}] (4; L=C7H4NS2). Compound 4 features a rare η(3)-interaction between rhodium and the B-C-C unit of a vinylborane moiety. Furthermore, with the objective of generating metallaboratranes of other early and late transition metals through a transmetallation approach, reactions of rhoda- and irida-boratrane complexes with metal carbonyl compounds were carried out. Although the objective of isolating such complexes was not achieved, several interesting mixed-metal complexes [{Cp*Rh}{Re(CO)3}(C7H4NS2)3] (5), [Cp*Rh{Fe2(CO)6}(μ-CO)S] (6), and [Cp*RhBH(L)2W(CO)5] (7; L=C7H4NS2) have been isolated. All of the new compounds have been characterized in solution by mass spectrometry, IR spectroscopy, and (1)H, (11)B, and (13)C NMR spectroscopies, and the structural types of 4-7 have been unequivocally established by crystallographic analysis.

Building upon the chemistry of Rh–N,S‐heterocyclic carbene complex, [(Cp*Rh)(L2)(1‐benzothiazol‐2‐ylidene)], 2 (Cp*=η5‐C5Me5; L=C7H4NS2) with various monoboranes‐Lewis adducts, we explored the chemistry of 2 with BH3⋅thf at elevated temperature. As a result, mild thermolysis of 2 with BH3⋅thf led to the formation of bis(sigma)borate [(η4‐C5Me5H)Rh(η2‐H3BL)], 3 and a bis‐zwitterionic species [Cp*RhS(BH2L2)], 4 with the concomitant release of BH3⋅bt (bt=benzothiazole). The RhS3C2N2B2 atoms in 4 generates two six membered rings fused by a common Rh−S bond, which may be considered as a bicycle [4.4.0] cage at the rhodium center. In an effort to generate the iridium analogue of 3, reaction of [Cp*IrCl2]2 with Na[H3B(mbt)] (mbt=2‐mercaptobenzothiazole) was carried out that produced bis(sigma)borate complex [(η4‐C5Me5H)Ir(η2‐H3BL)], 1. The solid state X‐ray structures of 1 and 3 showed that the Cp*H ligand coordinated to the metal center in a η4‐fashion. In compound 3, the methyl group is oriented towards rhodium center, whereas it is away from Ir center in 1. In addition, the DFT computations were performed to shed light on the bonding and electronic structures of these compounds.