Design Strategies for Luminescent Titanocenes: Improving the Photoluminescence and Photostability of Arylethynyltitanocenes.

Complexes that undergo ligand-to-metal charge transfer (LMCT) to d metals are of interest as possible photocatalysts. CpTi(CPh) (where CPh = phenylethynyl) was reported to be weakly emissive in room-temperature (RT) fluid solution from its phenylethynyl-to-Ti LMCT state but readily photodecomposes. Coordination of CuX between the alkyne ligands to give CpTi(CPh)CuX (X = Cl, Br) has been shown to significantly increase the photostability, but such complexes are not emissive in RT solution.

Photochemistry and Photophysics of Charge-Transfer Excited States in Emissive / Heterobimetallic Titanocene Tweezer Complexes.

Transition-metal complexes that undergo ligand-to-metal charge transfer (LMCT) to metals are of interest as possible photocatalysts due to the lack of deactivating d-d states. Herein, the synthesis and characterization of nine titanocene complexes of the formula CpTi(CAr)·MX (where Ar = phenyl, dimethylaniline, or triphenylamine; and MX = CuCl, CuBr, or AgCl) are presented. Solid-state structural characterization demonstrates that MX coordinates to the alkyne tweezers and CuX coordination has a greater structural impact than AgCl.

Delivery of Targeted Co(III)-DNA Inhibitors of Gli Proteins to Disrupt Hedgehog Signaling.

The Hedgehog (Hh) signaling pathway is integral for embryonic development and normal cell maintenance. However, aberrant expression of the Hh pathway is recognized as the oncogenic driving force for basal cell carcinoma (BCC). Current chemotherapeutic treatments that inhibit Hh signaling allow treatment of only locally advanced and metastatic BCCs via inhibition of the transmembrane protein, smoothened.

Ligand-to-Metal Charge-Transfer Photophysics and Photochemistry of Emissive d Titanocenes: A Spectroscopic and Computational Investigation.

Complexes with ligand-to-metal charge-transfer (LMCT) excited states involving d metals represent a new design for photocatalysts. Herein, the photochemistry and photophysics of d titanocenes of the type CpTi(CR), where CR = ethynylphenyl (CPh), 4-ethynyldimethylaniline (CDMA), or 4-ethynyltriphenylamine (CTPA), have been investigated. CpTi(CPh) and CpTi(CDMA) have also been characterized by single-crystal X-ray diffraction.

A Ln(III)-3-hydroxypyridine pH responsive probe optimized by DFT.

Differences in tissue pH can be diagnostic of cancer and other conditions that shift cell metabolism. Paramagnetic probes are promising tools for pH mapping in vivo using magnetic resonance spectroscopy (MRS) as they provide uniquely shifted MR signals that change with pH. Here, we demonstrate a 3-hydroxy-6-methylpyridyl coordinating group as a new pH-responsive reporter group for Ln(III) MRS probes.