Highly emissive, solution-processable and dynamic Eu(iii)-containing coordination polymers

Abstract

A new class of soluble Eu(III) coordination polymers based on a tridentate ditopic pybox ligand has been developed displaying high metal emission quantum yields of up to 73% as well as a unique dynamic behaviour in solution.

Real-time in situ monitoring via europium emission of the photo-release of antitumor cisplatin from a Eu–Pt complex

“…The design of our PtEuL complex is based on the unique photophysical properties of the lanthanide ions. 4 Owing to their forbidden f-f radiative transitions, appropriate organic antenna chromophores are required to absorb and transfer the photo-excitation energy to the lanthanide ions, thus amplifying their inherently weak but hypersensitive fingerprint emissions. 5 Our water-soluble and cell-permeable PtEuL complex is constructed from a Eu(III)-cyclen complex containing a rigid π-conjugated antenna chromophore with an isonicotinamide ligand which is coordinated to the cisplatin (Fig.…”

Looking for the Origin of Allosteric Cooperativity in Metallopolymers

“…Because of the predetermined optical and magnetic properties associated with their [Xe]4 f N electronic configurations ( N =0–14), the trivalent lanthanide cations, Ln 3+ , are attractive metallic partners for the design of application‐oriented Type III metallopolymers . However, the strict stoichiometry required for the formation of a well‐defined polymeric architecture in these systems prevents partial metallic occupancy or heterometallic loading without resorting to doping in random sites .…”

“…[21][22][23][24] Because of the predetermined optical and magnetic properties associatedw ith their [Xe]4 f N electronic configurations (N = 0-14), the trivalent lanthanide cations, Ln 3 + ,a re attractive met-allic partners for the design of application-orientedT ype III metallopolymers. [23][24][25][26] However,t he strict stoichiometry required for the formation of aw ell-defined polymerica rchitecture in these systemsp revents partial metallico ccupancy or heterometallic loading without resorting to doping in random sites. [27,28] On the contrary,t he less studied lanthanide-containing metallopolymers belonging to Type Ia nd Type II categories [5] are compatible with the complete or partial filling of the availables ites with one or different lanthanide complexes,t his without altering the polymeric structures ( Figure 1).…”

Synthesis and characterization of metallo-supramolecular polymers from thiophene-based unimers bearing pybox ligands

“…The tridentate ditopic pybox ligand has been partly described by A. Duerrbeck. 34 But, to the best of our knowledge, the synthesis, characterization and optical properties of a,u-bis(2,6bis(oxazoline-2-yl)pyridin-4-yl)thiophene (P-Th), a,u-bis(2,6bis(oxazoline-2-yl)pyridin-4-yl)bithiophene (P-Bt) and a,ubis(2,6-bis(oxazoline-2-yl)pyridin-4-yl)thieno[3,2-b]thiophene (P-Te) are new. Moreover, the process of self-assembly of the prepared unimers into MSPs by means of complexation with the selected model ion couplers, Fe 2+ , Zn 2+ , Ni 2+ , Cu 2+ , performed like a detailed properties survey, is also new.…”

“…Thiophene, bithiophene and thieno [3,2-b]thiophene linkers between pybox groups were chosen as competing units to phenyl linkers that were studied in the above mentioned work. 34 The incorporation of these units can positively inuence the photophysical and electrochemical properties due to a lower stiffness and a higher conjugation extent of the pybox based unimers used for MSP preparation. 42…”