Cage Metal Complexes

Cages vs. Prisms: Controlling the Formation of Metallosupramolecular Architectures with Ligand Side‐Chains

“…A unique feature of 1 is the presence of three bulky and rigid phenanthrene groups, which point away from the ligand center. Compared to other clathrochelate complexes described in the literature,, the conformational flexibility of the central part of complex 1 is particularly low. The rigidity of the core of complex 1 is evident when comparing its solid‐state structure (determined by X‐ray diffraction) with that of metalloligand 2 (Figure ).…”

“…For our investigations, we have prepared the new metalloligand 1 (Scheme ). This ligand contains an inert Fe II cage complex (′clathrochelate complex′), in its center, and it features four terminal 4‐pyridyl groups. The synthesis of 1 was accomplished in two steps.…”

Unexpected Side Products of Chemical Transformations in Cobalt(II) Pseudoclathrochelates: An X‐Ray Diffraction Study

“…Chemical design of these cobalt(II) pseudoclathrochelates is, however, a huge synthetic challenge, as only a boron capping atom ensures a TP coordination geometry of such complexes; otherwise, they have a trigonal‐antiprismatic (TAP, ϕ =60°) geometry unfavourable for their use as SMMs or paramagnetic probes for MRI . In addition, H‐bonded boron‐capped 3 d ‐metal pseudoclathrochelates (Scheme ) are only relatively stable, unlike their macropolycyclic analogues formed by covalent and strong coordination bonds, and can readily exchange pseudocapping H‐bonded species (Scheme ) or undergo intramolecular cyclization reactions (Scheme ) . As a result, optimization of the synthetic approaches towards these trigonal‐prismatic cobalt(II) complexes requires an insight into side products of their synthesis and their chemical transformations in different media.…”

Induced CD of iron(ii) clathrochelates: sensing of the structural and conformational alterations of serum albumins

“…17 A wide range of cage complexes with an encapsulated metal ion, known as clathrochelates, have been prepared and characterized to date. [18][19][20] Metal complexes of this type, which are formed by rigid quasiaromatic polyazomethine macropolycyclic ligands, are metal-centered compounds because their caging (encapsulating) ligands do not exist in the metal-free form due to thermodynamic reasons. 19 Iron(II) clathrochelates exhibit unique chemical and biological activities, and allow easy chemical modification of their macropolycyclic frameworks as molecular scaffolds.…”

“…[18][19][20] Metal complexes of this type, which are formed by rigid quasiaromatic polyazomethine macropolycyclic ligands, are metal-centered compounds because their caging (encapsulating) ligands do not exist in the metal-free form due to thermodynamic reasons. 19 Iron(II) clathrochelates exhibit unique chemical and biological activities, and allow easy chemical modification of their macropolycyclic frameworks as molecular scaffolds. Data on their biological activity as submicromolecular inhibitors in the transcription systems of T7 RNA and Taq DNA polymerases, [21][22][23][24][25] and as antifibrillogenic agents, [26][27][28] together with axially coordinated phthalocyanines, 29 were recently highlighted.…”