Superior Sensor for Be ²⁺ Ion Recognition via the Unprecedented Octahedral Crystal Structure of a One-Dimensional Coordination Polymer of Crown Fused Zinc Phthalocyanine

The unprecedented one-dimensional (1-D) coordination polymer of crown fused zinc phthalocyanine (P-CfZnPc) with an octahedral crystal structure and with intermolecular packing that has superior multichannel sensor ability for Be ²⁺ ion recognition was prepared and characterized by single-crystal X-ray diffraction analysis (XRD) and a wide range of spectroscopic and voltammetric methods. An exceptional feature of the crystal structure of P-CfZnPc is that each zinc ion in the phthalocyanine (Pc) polymer is coordinated by the four isoindole nitrogen atoms and an outer oxygen atom of the Pc molecule. This structure is the first example of an octahedral arrangement in a 1-D polymeric chain for zinc phthalocyanines (ZnPcs) and zinc porphyrins (ZnPs) reached without the presence of a coordinating solvent, which was confirmed by XRD analysis. Interestingly, this (1-D) coordination polymer preserves its conformation in THF (tetrahydrofuran) solution, thereby effectively preventing aggregation. This result was confirmed by the particle size of the molecule (125 nm) using dynamic light scattering (DLS) and matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectra as well as UV-vis spectroscopy. The sensor has long-term stability (more than 3 months in solution), a very low response time (less than 1 s), and nonaggregating ability, facilitating the accurate determination of ultra-trace amounts of Be ²⁺ (lower than 1 ppb), which is extremely important in terms of human health and environmental protection. The sensor can highly selectively and sensitively bind Be ²⁺ among Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Al ³⁺ , Co ²⁺ , Hg ²⁺ , Ni ²⁺ , Pb ²⁺ , and Zn ²⁺ ions via Be ²⁺ -induced J aggregation of Pc molecules. Such a binding leads to not only a significant decrease in Pc absorption (677 nm) as well as the creation of new absorption (720 nm) but also fluorescence emission quenching (690 nm). Furthermore, the sensor displayed highly selective voltammetric recognition for Be ²⁺ following J aggregation/disaggregation in the second reduction process. The binding mechanism of the sensor and Be ²⁺ ion was also explained on the basis of TD-DFT calculations.