Photosynthesis is ap rocess wherein the chromophores in plants and bacteria absorb light and convert it into chemical energy.T om imic this process,a ne missive poly(ethylene glycol)-decorated tetragonal prismatic platinum(II) cage was prepared and used as the donor molecule to construct al ight-harvesting system in water.E osin Yw as chosen as the acceptor because of its good spectral overlap with that of the metallacage,w hich is essential for the preparation of lightharvesting systems.S uchacombination showed enhanced catalytic activity in catalyzing the cross-coupling hydrogen evolution reaction, as compared with eosin Yalone.This study offers ap athway for using the output energy from the lightharvesting system to mimic the whole photosynthetic process.Photosynthesis, [1] as the primary source for the fuel on earth, is ap rocess by which living plants and bacteria absorb, capture,t ransfer, and store energy from the sun. In this process,the energy from sunlight is captured and funneled by adense array of chlorophyll molecules to the reaction center, and then converted into chemical energy. [2] So far, many artificial light-harvesting systems mimicking this process have been developed by using aF çster resonance energy-transfer (FRET) process,w ith the aim of developing clean and sustainable energy. [3][4][5] Among them, supramolecular systems [5] have received considerable attention not only because of their tunable and functionable molecular structures but also because the energy transfer between chlorophyll and protein in natural systems also relies on supramolecular selfassembly.F or example,Y ang et al. developed ah ighly efficient light-harvesting system based on the self-assembly of organic nanocrystals. [5b] Wang, Hu, and co-workers reported light-harvesting systems formed by water-soluble pillar[6]arene-based host-guest interactions. [5g] However, most of these systems just mimicked the FRET process of natural systems.T he use of the output energy for photocatalytic reactions has been rarely addressed. As natural photosynthetic systems also use the transferred energy for chemical reactions,artificial light-harvesting systems with the ability to catalyze chemical reactions for storing and releasing chemical energy are urgently needed.Metal-organic cages and metallacages [6] represent threedimensional cagelike structures formed by metal-coordination-driven self-assembly.W ith precisely controlled inner cavities,such fascinating structures have been widely studied in the past three decades for guest encapsulation, catalysis, and stabilizing reactive intermediates,e tc. [7] Recently,S tang et al. developed as eries of emissive metallacages [8] through the incorporation of tetraphenylethylene (TPE) derivatives as the building blocks.T hese metallacages exhibited aggregation-induced emission (AIE) properties [9] because of the restriction of molecular motions that decrease the nonradiative decay.Inartificial light-harvesting systems,thousands of donor molecules are generally used for asingle acceptor,...

It is quite challenging to realize fluorescence resonance energy transfer (FRET) between two chromophores with specific positions and directions. Herein, through the self-assembly of two carefully selected fluorescent ligands via metal-coordination interactions, we prepared two tetragonal prismatic platinum(II) cages with a reverse FRET process between their faces and pillars. Bearing different responses to external stimuli, these two emissive ligands are able to tune the FRET process, thus making the cages sensitive to solvents, pressure, and temperature. First, these cages could distinguish structurally similar alcohols such as n-butanol, t-butanol, and ibutanol. Furthermore, they showed decreased emission with bathochromic shifts under high pressure. Finally, they exhibited a remarkable ratiometric response to temperature over a wide range (223-353 K) with high sensitivity. For example, by plotting the ratio of the maximum emission (I 600 /I 480 ) of metallacage 4b against the temperature, the slope reaches 0.072, which is among the highest values for ratiometric fluorescent thermometers reported so far. This work not only offers a strategy to manipulate the FRET efficiency in emissive supramolecular coordination complexes but also paves the way for the future design and preparation of smart emissive materials with external stimuli responsiveness.

Photosynthesis is a process wherein the chromophores in plants and bacteria absorb light and convert it into chemical energy. To mimic this process, an emissive poly(ethylene glycol)‐decorated tetragonal prismatic platinum(II) cage was prepared and used as the donor molecule to construct a light‐harvesting system in water. Eosin Y was chosen as the acceptor because of its good spectral overlap with that of the metallacage, which is essential for the preparation of light‐harvesting systems. Such a combination showed enhanced catalytic activity in catalyzing the cross‐coupling hydrogen evolution reaction, as compared with eosin Y alone. This study offers a pathway for using the output energy from the light‐harvesting system to mimic the whole photosynthetic process.

Multicomponent coordination‐driven self‐assembly has proved to be a convenient approach to prepare advanced supramolecular coordination complexes (SCCs), especially for those with three‐dimensional structures. Herein, we report the preparation of three tetragonal prismatic cages via the self‐assembly of Pt(PEt3)2(OTf)2, three different linear dipyridyl ligands and porphyrin‐based sodium benzoate ligands. Due to the efficient charge separation in the coordination process of Pt(PEt3)2(OTf)2 with pyridine and carboxylic acid and the directionality of metal‐coordination bonds, these cages were prepared in high isolated yields (more than 90 %). The absorption and emission properties as well as the singlet oxygen quantum yields of these cages were also studied, showing their potential applications as contrast agents for bio‐imaging and photosensitizers for photodynamic therapy.