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From Chain‐ to Graphene‐like Hydroxyl‐terminated (ZnO)n Clusters with n≤6 Obtained via Zinc Dimethoxide Hydrolysis and Condensation: Ab initio Structural, Electronic, Vibrational and Optical Properties Calculations

“…One case corresponds to a “linear” trimer (named C l ) and the other case corresponds to a “bended” trimer (named C b ) as shown in Figure 7c, with associated trimerization free energies of −0.52 and −0.60 eV, respectively, as shown in Figure 8c. The formation of the double type ‐C bonding, at least in a linear fashion, is also consistent with the planar μ 3 ‐O oxo‐bridge observed experimentally for a zinc‐oxo cluster with bulky substituents [79] . The trimer subsequent cyclization reactions were studied for the most stable; i. e. n =3(C b ) cluster, for its first, second, third and fourth dehydration products, as depicted in Figure 7c.…”

“…[60] Experimentally, the formation of type-C bonding was observed in the form of a Zn-ring(ZnO) 2 À Zn subunit (also known as planar μ 3 -O oxo-bridge) for a zinc-oxo cluster with bulky substituents. [79] Our calculations indicate that, at least in the gas phase, any of the three n = 2(A), n = 2(B) and n = 2(C) dimers in the chain-like fashion are thermodynamically more stable than the first cyclization product of cube-like double dimeric zinc dihydroxide (Figure S2a) by 0.41, 0.52 and 0.65 eV, respectively. Before continuing with the trimerization stage, the dimer subsequent cyclization reactions were studied following two possible routes as depicted in Figure 7b.…”

“…The formation of a dimer via type ‐C bonding named “double‐dimer” was predicted theoretically to be thermodynamically favorable via condensation of two dimeric methyl zinc hydroxide clusters [60] . Experimentally, the formation of type ‐C bonding was observed in the form of a Zn‐ ring (ZnO) 2 −Zn subunit (also known as planar μ 3 ‐O oxo‐bridge) for a zinc‐oxo cluster with bulky substituents [79] . Our calculations indicate that, at least in the gas phase, any of the three n =2(A), n =2(B) and n =2(C) dimers in the chain‐like fashion are thermodynamically more stable than the first cyclization product of cube‐like double dimeric zinc dihydroxide (Figure S2a) by 0.41, 0.52 and 0.65 eV, respectively.…”

“…The formation of the double type-C bonding, at least in a linear fashion, is also consistent with the planar μ 3 -O oxo-bridge observed experimentally for a zinc-oxo cluster with bulky substituents. [79] The trimer subsequent cyclization reactions were studied for the most stable; i. e. n = 3(C b ) cluster, for its first, second, third and fourth dehydration products, as depicted in Figure 7c.…”

Zinc oxide clusters encapsulated by organozinc phosphazenate assemblies

“…1). These include Zn 2 O (a) [4], Zn 3 O (b) [5], Zn 4 O (c) [6], Zn 4 O 2 (e) [7], Zn 6 O 2 (f) [8] and Zn 7 O 2 (g) [9,10]. None of the known complexes bearing zinc oxide clusters contain more than two oxide centres.…”