An Unexpected Photoelectronic Effect from [Co(en)₃]₂(Zr₂F₁₂)(SiF₆)⋅4 H₂O, a Compound Containing an H‐Bonded Assembly of Discrete [Co(en)₃]³⁺, (Zr₂F₁₂)⁴⁻, and (SiF₆)²⁻ Ions

Abstract

Hydrogen‐bonded network: A hydrothermal synthesis delivers the titled compound, which consists of an H‐bonded network of discrete [Co(en)3]3+, (Zr2F12)4−, and (SiF6)2− ions. It exhibits an unexpected photoelectronic effect in the near‐UV region (see figure).

The [U2F12]2− Anion of Sr[U2F12]

“…To our knowledge, there are so far only two reported cases with condensed homoleptic complex anions exhibiting a coordination number of seven for their central atoms. One being the [Zr 2 F 12 ] 4− anion ( Ci symmetry) in [Co(en) 3 ] 2 [Zr 2 F 12 ][SiF 6 ]⋅4 H 2 O, which can be described as a distorted edge‐linked pentagonal bipyramid . The other case can be described as an association of two [IF 6 ] − anions in [N(Me) 4 ][IF 6 ], forming a [I 2 F 12 ] 2− anion, which consists of edge‐sharing monocapped trigonal prisms ( Ci symmetry).…”

[H3tren]3+ and [H4tren]4+ fluoride zirconates or tantalates

“…3). It must be noted that such isolated dimers are not very frequently encountered in hybrid fluorides [21][22][23][24][25].…”

Organometallic complexes as anion hosts

“…Hydrogen bonds between chelated diamines and polar molecules have been proposed to stabilize the transition state in hydrogen transfer to ketones mediated by Noyori-type catalysts 39 and to determine the nucleobase preferences of anti-cancer Sadler's areneruthenium complexes. 40 In the solid state, interactions between ethylenediamine (en) N-H groups and terephthalate (tph) oxygens link the chains of [Zn(en)(tph)] ' polymers, 41 42 Hydrogen bonds between N-H groups of 1,2-phenylenediamine (phda) and the keto oxygens of the ester groups determine the observed conformation of [Mo(CO) 2 L(phda)] (L = dimethyl fumarate or maleate) complexes. 43 As a very simple model where such weak interactions with external anions could be examined isolated from other stronger interactions, we synthesized the new compound [Re(CN t Bu)(CO) 3 (phda)]BAr 4 9 by the reaction sequence displayed in Scheme 5.…”