Yanxia Zhao

Synthesis and Reactivity of Nickel Hydride Complexes of an α‑Diimine Ligand

Reaction of L(0)NiBr(2) with 2 equiv of NaH yielded the Ni(II) hydride complex [(L(•-))Ni(μ-H)(2)Ni(L(•-))] (1) (L = [(2,6-iPr(2)C(6)H(3))NC(Me)](2); L(0) represents the neutral ligand, L(•-) is its radical-anionic form, and L(2-) denotes the dianion) in good yield. Stepwise reduction of complex 1 led to a series of nickel hydrides. Reduction of 1 with 1 equiv of sodium metal afforded a singly reduced species [Na(DME)(3)][(L(•-))Ni(μ-H)(2)Ni(L(•-))] (2a) (DME = 1,2-dimethoxyethane), which contains a mixed-valent core [Ni(μ-H)(2)Ni](+). With 2 equiv of Na a doubly reduced species [Na(DME)](2)[L(2-)Ni(μ-H)(2)NiL(2-)] (3a) was obtained, in which each monoanion (L(•-)) in the precursor 1 has been reduced to L(2-). By using potassium as the reducing agent, two analogous species [K(DME)(4)][(L(•-))Ni(μ-H)(2)Ni(L(•-))] (2b) and [K(DME)](2)[L(2-)Ni(μ-H)(2)NiL(2-)] (3b) were obtained. Further treatment of 3b with 2 equiv of K led to a trinuclear complex [K(DME)(THF)](2)K(2)[L(2-)Ni(μ-H)(2)Ni(μ-H)(2)NiL(2-)] (4), which contains one Ni(II) and two Ni(I) centers with a triplet ground state. When 1 and 3a were warmed in toluene or benzene, respectively, three reverse-sandwich dinickel complexes, [(L(•-))Ni(μ-η(3):η(3)-C(7)H(8))Ni(L(•-))] (5) and [Na(DME)](2)[L(2-)Ni(μ-η(3):η(3)-C(6)H(5)R)NiL(2-)] (6: R = CH(3); 7: R = H), were isolated. Reaction of 1 with Me(3)SiN(3) gave the N(3)-bridged complex [(L(•-))Ni(μ-η(1)-N(3))(2)Ni(L(•-))] (8). The crystal structures of complexes 1-8 have been determined by X-ray diffraction, and their electronic structures have been fully studied by EPR/NMR spectroscopy.

Encapsulation of Halocarbons in a Tetrahedral Anion Cage

Caged supramolecular systems are promising hosts for guest inclusion, separation, and stabilization. Well-studied examples are mainly metal-coordination-based or covalent architectures. An anion-coordination-based cage that is capable of encapsulating halocarbon guests is reported for the first time. This A4L4-type (A=anion) tetrahedral cage, [(PO4)4L4](12-), assembled from a C3-symmetric tris(bisurea) ligand (L) and phosphate ion (PO4(3-)), readily accommodates a series of quasi-tetrahedral halocarbons, such as the Freon components CFCl3, CF2Cl2, CHFCl2, and C(CH3)F3, and chlorocarbons CH2Cl2, CHCl3, CCl4, C(CH3)Cl3, C(CH3)2Cl2, and C(CH3)3Cl. The guest encapsulation in the solid state is confirmed by crystal structures, while the host-guest interactions in solution were demonstrated by NMR techniques.

Alkali Metal and Zinc Complexes of a Bridging 2,5-Diamino-1,4-Benzoquinonediimine Ligand

Two alkali metal complexes of a bridging 2,5-diamino-1,4-benzoquinonediimine ligand (dipp-dabqdiH(2)), [(thf)(2)Li(μ-dipp-dabqdi)Li(thf)(2)] (1) and [(dme)(1.5)Na(μ-dipp-dabqdi)Na(dme)(1.5)](n) (2, dme = 1,2-dimethoxyethane), have been synthesized by the reaction of dipp-dabqdiH(2) with Li(n)Bu or sodium metal. In addition, treatment of 1,2,4,5-tetrakis(2,6-diisopropylamino)benzene (dipp-tabH(4)) with potassium metal in dme afforded the complex [(dme)(2)K(μ-dipp-tabH(2))K(dme)(2)] (3). X-ray crystal diffraction analyses revealed that complexes 1 and 3 have dinuclear structures, while the sodium complex 2 aggregates to a one-dimensional polymer through bridging dme ligands. With increasing ion radius, the coordination number of the alkali metal (Li, Na, and K) increases from four to five to six, while the coordination geometry changes from distorted tetrahedral to square pyramidal and further to octahedral in 1, 2, and 3, respectively. The salt metathesis reactions of 1 and 2 with anhydrous ZnCl(2) yielded the ion-contacted zinc complexes [(thf)(3)Li(μ-Cl)ClZn(μ-dipp-dabqdi)ZnCl(μ-Cl)Li(thf)(3)] (4), [(dme)(2)Li(μ-Cl)ClZn(μ-dippdabqdi)ZnCl(μ-Cl)Li(dme)(2)] (5), and [(dme)(2)Na(μ-Cl)(2)Zn(μ-dipp-dabqdi)Zn(μ-Cl)(2)Na(dme)(2)] (6), respectively. The ligand exists as the dianionic form in compounds 1-6 upon double deprotonation, and a complete electronic delocalization (except for 3) of the quinonoid π-system is observed between the metal centers over the two N═C-C═C-N halves of the ligand. The electronic structures of the complexes were studied by density functional theory (DFT) computations.

Tris Chelating Phosphate Complexes of Bis(thio)urea Ligands

Two bisurea (L(1), L(2)) and one bisthiourea (L(3)) ligands were synthesized and their anion coordination behavior was studied. These ligands can readily form the tris chelates [PO4(L)3](3-) (1, 5, and 6) with phosphate ion (PO4(3-)) in the solid state, in which the anion is coordinated by six urea groups through 12 hydrogen bonds. Solution binding studies by (1)H NMR and UV-vis spectroscopy revealed different binding properties of the ligands toward phosphate ion. While the bis(p-nitrophenyl)-substituted bisurea L(1) retains the 3:1 (host to guest) binding ratio in solution, the diethyl derivative L(2) only forms 1:1 complex with phosphate ion. The more acidic thiourea L(3) undergoes deprotonation/decomposition in the presence of phosphate ion. Moreover, the sulfate complex (2) of L(1) and bicarbonate (3) and carbonate (4) complexes of L(2) have also been obtained, which show lower coordination numbers both in the solid state and in solution.

Cucurbit[10]uril-Based [2]Rotaxane: Preparation and Supramolecular Assembly-Induced Fluorescence Enhancement

As the cucurbit[n]uril (CB[n]) homologue with the largest cavity size, cucurbit[10]uril (CB[10]) can encapsulate big guests to form interesting host-guest complexes/assemblies. Herein, we report the preparation and fluorescence properties of CB[10]-based [2]rotaxane (CB[10]·1) formed from cucurbit[10]uril and dumbbell-like guest 1. This [2]rotaxane (CB[10]·1) is assembled by C═O···N+ ion-dipole interactions between oxygen atoms of the carbonyl fringed portals of CB[10] and the positively charged pyridinium units of 1 via the slipping method under heating at 95 °C in DMSO. In contrast, other cucurbit[n]uril (CB[n], n = 6-8) homologues cannot form rotaxanes with 1 due to their smaller cavities. The dumbbell-like guest 1 is a poor emitter in DMSO. Interestingly, the formation of CB[10]·1 renders the restriction of intramolecular rotation of TPE, which features a strong fluorescent intensity, long lifetime, and high quantum yield. Furthermore, CB[10]·1 is shown to aggregate plate-like structures with various sizes in different solvents (DMSO, THF, or CHCl3), resulting in a stepwise aggregation-induced emission enhancement effect. This kind of CB[10]-based [2]rotaxane may be used to fabricate luminescent systems with unique emission properties.

Anion binding of tris-(thio)urea ligands

Two tridentate tris-(thio)urea ligands (L2 and L3) have been synthesized. Ligand L2 forms a 2 : 2 complex (1) with the (H2PO4·HPO4)3– dimer. 1H NMR and UV-vis titrations revealed that the mixed urea–thiourea ligand, L2, shows considerable anion binding affinities, while the tris-thiourea ligand, L3, undergoes deprotonation in the presence of basic anions.

Multinuclear Alkali Metal Complexes of a Triphenylene-Based Hexamine and the Transmetalation to Tris(N-heterocyclic tetrylenes) (Ge, Sn, Pb)

A C3-symmetric hexamine (LH6) based on the triphenylene and ortho-phenylenediamine (PDAH2) skeletons has been synthesized, and was partially or fully deprotonated upon treatment with alkali metal agents to afford amino-amido or diamido coordination sites. Four alkali metal complexes, the dinuclear [Na2(LH4)(DME)5] (1) and [K2(LH4)(DME)4] (2), trinuclear [K3(LH3)(DME)6] (3), and hexanuclear [Li6(L)(DME)6] (4), were obtained and used in transmetalation/ligand exchange with other metals. The hexalithium salt of the fully deprotonated ligand, [Li6L], reacted with heavier group 14 element halides to yield three tris(N-heterocyclic tetrylenes), the germylene [Ge3(L)] (5), stannylene [Sn3(L)] (6), and plumbylene [Pb3(L)] (7). The synthesis and crystal and electronic structures of these compounds are reported.

Supramolecular organic frameworks of cucurbit[n]uril-based [2]pseudorotaxanes in the crystalline state

Three novel supramolecular organic frameworks (SOFs) were constructed from cucurbit[n]uril-based [2]pseudorotaxanes by orthogonal and/or parallel π–π interactions between 4,4′-bipyridin-1-ium units. In the crystal structure, [2]pseudorotaxane (CB[6]·1) formed an interwoven Chinese knot-like framework with high thermal stability.

Mono‐ and Dinuclear Heteroleptic Cobalt Complexes with α‐Diimine and Polyarene Ligands

Reactions of the dimeric cobalt complex [(L(-) Co)2 ] (1, L=[(2,6-iPr2 C6 H3 )NC(Me)]2 ) with polyarenes afforded a series of mononuclear and dinuclear complexes: [LCo(η(4) -anthracene)] (2), [LCo(μ-η(4) :η(4) -naphthalene)CoL] (3), and [LCo(μ-η(4) :η(4) -phenanthrene)CoL] (4). The pyrene complexes [{Na2 (Et2 O)2 }{LCo(μ-η(3) :η(3) -pyrene)CoL}] (5) and [{Na2 (Et2 O)3 }{LCo(η(3) -pyrene)}] (6) were obtained by treating precursor 1 with pyrene followed by reduction with Na metal. These complexes contain three potential redox active centers: the cobalt metal and both α-diimine and polyarene ligands. Through a combination of X-ray crystallography, EPR spectroscopy, magnetic susceptibility measurement, and DFT computations, the electronic configurations of these complexes were studied. It was determined that complexes 2-4 have a high-spin Co(I) center coupled with a radical α-diimine ligand and a neutral polyarene ligand. Whereas, the ligand L in complexes 5 and 6 has been further reduced to the dianion, the cobalt remains in a formal (I) oxidation state, and the pyrene molecule is either neutral or monoanionic.

Cycloaddition versus Cleavage of the C=S Bond of Isothiocyanates Promoted by Digallane Compounds with Noninnocent α-Diimine Ligands

Whereas the chemistry of single-bond activation by compounds of the main group elements has undergone some development in recent years, the cleavage of multiple bonds remains underexplored. Herein, the reactions of two digallanes bearing α-diimine ligands, namely, [L1 Ga-GaL1 ] (1, L1 =dpp-dad=[(2,6-iPr2 C6 H3 )NC(CH3 )]2 ) and [L2 Ga-GaL2 ] (2, L2 =dpp-bian=1,2-[(2,6-iPr2 C6 H3 )NC]2 C10 H6 ), with isothiocyanates are reported. Reactions of 1 or 2 with isothiocyanates in 1:2 molar ratio proceeded with [2+4] cycloaddition of the C=S bond across the C2 N2 Ga metallacycle with formation of C-C and S-Ga single bonds to afford [L1 (RN=C-S)Ga-Ga(S-C=NR)L1 ] (3, R=Me; 4, R=Ph) and [L2 (RN=C-S)Ga-Ga(S-C=NR)L2 ] (8, R=allyl; 9, R=Ph). In the cases of 8 and 9, this cycloaddition is reversible. The digallanes reacted with 2 equiv of PhNCS in the presence of Na metal or at high temperatures through a unique reductive cleavage of the C=S bond to yield the disulfide-bridged digallium species [Na(THF)3 ]2 [L1 Ga(μ-S)2 GaL1 ] (5), [L2 Ga(μ-S)2 GaL2 ] (10), and [Na(DME)3 ][L2 Ga(μ-S)2 GaL2 ] (11). Moreover, products 4 and 5 can further react with an excess of isothiocyanate, through cleavage of the C=S bond or cycloaddition, to give the bis- or mono-S-bridged complexes [Na(THF)2 ]2 [L1 (PhN=C-S)Ga(μ-S)2 Ga(S-C=NPh)L1 ] (6) and [L1 (PhN=C-S)Ga(μ-S)Ga(S-C=NPh)L1 ] (7). All the newly prepared compounds were characterized by elemental analysis, single-crystal X-ray diffraction, IR spectroscopy, NMR (3-9) or ESR spectroscopy (11), and DFT calculations.