Nonperipheral Tetrakis(dibutylamino)phthalocyanines. New Types of 1,8,15,22-Tetrakis(substituted)phthalocyanine Isomers

Cyclic tetramerization of 3-(dibutylamino)­phthalonitrile in refluxing <i>n</i>-pentanol in the presence of magnesium pentanoate afforded the four regioisomer-containing nonperipheral 1,8-/11,15-/18,22-/25-tetrakis­(dibutylamino)­phthalocyaninato magnesium complexes with the 1,8,15,22-tetrakis­(dibutylamino)­phthalocyanine isomer Mg­{Pc­[α-N­(C₄H₉)₂]₄-<i>C</i>₄} (<b>2</b>). This, in combination with its much superior crystallinity over the remaining three isomers, renders the easy isolation of <b>2</b> only through two simple recrystallizations from THF and methanol. Treatment of <b>2</b> with trifluoroacetic acid induced the isolation of metal-free 1,8,15,22-tetrakis­(dibutylamino)­phthalocyanine, H₂{Pc­[α-N­(C₄H₉)₂]₄-<i>C</i>₄} (<b>1</b>), which further reacted with M­(OAc)₂·<i>n</i>H₂O (M = Ni, Zn) in refluxing <i>n</i>-pentanol, giving the 1,8,15,22-tetrakis­(dibutylamino)­phthalocyaninato metal complexes M­{Pc­[α-N­(C₄H₉)₂]₄-<i>C</i>₄} (M = Ni (<b>3</b>), Zn (<b>4</b>)). The full series of four 1,8,15,22-tetrakis­(dibutylamino)­phthalocyanine isomeric compounds have been characterized by a series of spectroscopic methods and single-crystal X-ray diffraction analyses. Obviously, the present result provides a simple and effective pathway for the synthesis and isolation of novel 1,8,15,22-tetrakis­(dibutylamino)­phthalocyanine isomeric derivatives, providing one step forward toward completing bis­(alkyl)­amino-incorporated phthalocyanine species

Efficient Flexible Counter Electrode Based on Modified Graphite Paper and in Situ Grown Copper Sulfide for Quantum Dot Sensitized Solar Cells

Flexible counter electrode (CE) plays an important role in portable quantum dot sensitized solar cells (QDSCs). However, the present power conversion efficiency (PCE) of bendable QDSC is rather limited partly due to the unsatisfactory conductivity, flexibility, catalytic activity, and fabrication technique of CE. In this work, flexible CEs composed of Cu_<i>x</i>S and graphite paper (GP) are built and fabricated through a facile successive ionic layer adsorption reaction (SILAR) method. Through designing and optimizing of the surface property of GP, coverage, and thickness of catalyst, excellently performed CEs are achieved with the maximal PCE of 8.70% under one full sun illumination for Zn–Cu–In–Se QDSCs. Further, fully flexible QDSCs assembled with the as-prepared CEs and plastic photoanodes show a high PCE of 2.45% under the same illumination

Fluorescent Phthalocyanine–Graphene Conjugate with Enhanced NIR Absorbance for Imaging and Multi-Modality Therapy

There has been increasing interest in design theranostic agents for combining diagnosis and different treatment modalities, especially for development physiological stable materials to avoid instability and dissociation in biological environment. Herein, a covalently connected silicon phthalocyanine (SiPc) and graphene oxide (GO) conjugate SiPc-GO is designed and synthesized via conjugation reaction to render stability. This novel highly water-soluble material displays intrinsically fluorescence and synchronous photothermal-photodynamic therapy (PTT/PDT) effect, along with 3-fold higher near-infrared (NIR) absorbance comparing to pristine GO. In vitro cell studies show that SiPc-GO could cause intracellular fluorescence, photothermal effect and reactive oxygen species (ROS) generation synchronously, and effective photoablation of cancer cells could be triggered by both 671 and 808 nm lasers via synergistic PTT/PDT or NIR photothermal effects, respectively. In vivo systemic administration in MCF-7 xenograft mice shows that SiPc-GO could effectively accumulate in the tumor regions and induce the inhibition of tumor growth violently after laser irradiation. This work establish SiPc-GO as a multimodality nanosized photomedicine for cancer imaging, synergistic PTT/PDT, and NIR photothermal therapy