Aggregation‐Induced Emission and Aggregation‐Promoted Photo‐oxidation in Thiophene‐Substituted Tetraphenylethylene Derivative

Aggregation‐induced emission combined with aggregation‐promoted photo‐oxidation has been reported only in two works quite recently. In fact, this phenomenon is not commonly observed for AIE‐active molecules. In this work, a new tetraphenylethylene derivative (TPE‐4T) with aggregation‐induced emission (AIE) and aggregation‐promoted photo‐oxidation was synthesized and investigated. The pristine TPE‐4T film exhibits strong bluish‐green emission, which turns to quite weak yellow emission after UV irradiation. Interestingly, after solvent treatment, the weakly fluorescent intermediate will become bright‐yellow emitting. Moreover, the morphology of the TPE‐4T film could be regulated by UV irradiation. The wettability of the TPE‐4T microcrystalline surface is drastically changed from hydrophobic to hydrophilic. This work contributes a new member to the aggregation induced photo‐oxidation family and enriches the photo‐oxidation study of tetraphenylethylene derivatives.     

Stimuli‐responsive antifouling polyisobutylene‐based biomaterials via modular surface functionalization

This article demonstrates a new, modular approach to surface functionalization that harnesses chain entanglement. A layer of functionalized polyisobutylene, (PIB)‐ω, where ω = ‐OH, ‐thymine (T), ‐hexaethylene glycol (HEG), poly(ethylene glycol) (‐PEG‐OH), methoxy‐functionalized poly(ethylene glycol) (‐PEG‐OCH₃), and ‐tetraethylene glycol‐α‐lipoate (TEG‐αL) was adhered to PIB‐based thermoplastic elastomer (TPE) surfaces. X‐ray photoelectron spectroscopy (XPS) at angles ranging from 20° to 75° showed decreasing polar group concentration with increasing penetration depth, confirming segregation of polar groups toward the surface. Water contact angle (WCA) of the PIB‐based TPE dropped from 95° to 79°?83° upon coating, and soaking in water for 24 h further decreased the WCA. Dynamic WCA measurements showed 40–30° receding angles, showing that stimulus from an aqueous environment elicits enrichment of polar groups on the surface. Fibrinogen (Fg) adsorption on the various surfaces was quantified using surface plasmon resonance (SPR). Static and dynamic WCA did not vary significantly among TPE + PIB‐ω surfaces, but there were dramatic differences in Fg adsorption: 256 ng/cm² was measured on the native TPE, which dropped to 40 and 22 ng/cm² on PIB‐PEG‐OCH₃ and PIB‐PEG‐OH‐coated surfaces. PIB‐TEG‐αL‐coated surfaces presented the lowest Fg adsorption with 14 ng/cm². © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1742–1749     

Effect of the Counterion on Light Emission: A Displacement Strategy to Change the Emission Behaviour from Aggregation‐Caused Quenching to Aggregation‐Induced Emission and to Construct Sensitive Fluorescent Sensors for Hg2+ Detection

In this paper, a simple strategy to change the emission behaviour of luminogenic materials was developed. Tetraphenylethene (TPE)‐functionalised benzothiazolium salts with different counteranions (TPEBe?X; X=I^?, ClO₄^? and PF₆^?) were designed and synthesised. All the luminogens show weak red emission in the solution state that originates from intramolecular charge transfer from TPE to the benzothiazolium unit. Whereas aggregate formation enhances the light emission of TPEBe?ClO₄ and TPEBe?PF₆, that of TPEBe?I is quenched, thus demonstrating the phenomena of aggregation‐induced emission and aggregation‐caused quenching. TPEBe?I works as a light‐up fluorescent sensor for Hg²⁺ in aqueous solution with high sensitivity and specificity owing to the elimination of the emission quenching effect of the iodide ion by the formation of HgI₂ as well as the induction in aggregate formation by the complexation of Hg²⁺ with the S atom of the benzothiazolium unit of TPEBe?I. A solid film of TPEBe?I was prepared that can monitor the level of Hg²⁺ in aqueous solution with a detection limit of 1 μM .     

Decomposition‐Assembly of Tetraphenylethylene Nanoparticles With Uniform Size and Aggregation‐Induced Emission property

Tetraphenylethylene (TPE)‐substituted poly(allylamine hydrochloride) (PAH‐g‐TPE) is synthesized by a Schiff base reaction between PAH and TPE‐CHO. The PAH‐g‐TPE forms micelles in water at pH 6, which are further transformed into pure TPE‐CHO nanoparticles (NPs) with a diameter of ≈300 nm after incubation in a solution of low pH value. In contrast, only amorphous precipitates are obtained when TPE‐CHO methanol solution is incubated in water. The aggregation‐induced emission feature of the TPE molecule is completely retained in the TPE NPs, which can be internalized into cells and show blue fluorescence. Formation mechanism of the TPE NPs is proposed by taking into account the guidance effect of linear and charged PAH molecules, and the propeller‐stacking manner between the TPE‐CHO molecules.     

Synthesis of poly[N‐isopropylacrylamide‐g‐poly(ethylene glycol)] with a reactive group at the poly(ethylene glycol) end and its thermosensitive self‐assembling character

Poly[N‐isopropylacrylamide‐g‐poly(ethylene glycol)]s with a reactive group at the poly(ethylene glycol) (PEG) end were synthesized by the radical copolymerization of N‐isopropylacrylamide with a PEG macromonomer having an acetal group at one end and a methacryloyl group at the other chain end. The temperature dependence of the aqueous solutions of the obtained graft copolymers was estimated by light scattering measurements. The intensity of the light scattering from aqueous polymer solutions increased with increasing temperature. In particular, at temperatures above 40°C, the intensity abruptly increased, indicating a phase separation of the graft copolymer due to the lower critical solution temperature (LCST) of the poly(N‐isopropylacrylamide) segment. No turbidity was observed even above the LCST, and this suggested a nanoscale self‐assembling structure of the graft copolymer. The dynamic light scattering measurements confirmed that the size of the aggregate was in the range of several tens of nanometers. The acetal group at the end of the PEG graft chain was easily converted to the aldehyde group by an acid treatment, which was analyzed by ¹H NMR. Such a temperature‐induced nanosphere possessing reactive PEG tethered chains on the surface is promising for new nanobased biomedical materials. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1457–1469, 2006     

Pyridinium‐Substituted TetraphenylethyleneEntailing Alkyne Moiety: Enhancement of Photosensitizing Efficiency and Antimicrobial Activity

Apart from sensing and imaging, luminogens with aggregation‐induced emission (AIE) are also interesting for photosensitizing. The photosensitizing behavior and bacteria‐killing performance of a pyridinium‐substituted tetraphenylethylene with an alkyne group ( TPE‐A‐Py⁺ ) is reported herein. Interestingly, TPE‐A‐Py⁺ exhibits higher photosensitizing efficiency than TPE‐Py⁺ (without alkyne group) when I⁻ was used as a counteranion. This is well explained by the fact that the ΔΕ _ST between the excited singlet state (S ₁) and triplet state (T ₁) was lower for TPE‐A‐Py⁺ than for TPE‐Py⁺ , according to theoretical calculations. Moreover, replacement of I ⁻ with other anions (PF₆⁻, N(SO₂CF₃)₂⁻ and BPh₄⁻) led to a decrease of photosensitizing efficiency for TPE‐A‐Py⁺ . Notably, TPE‐A‐Py⁺ could be used as an efficient photosensitizer to photo‐inactivate ampicillin‐resistant (amp^r) E. coli at low concentration under white‐light irradiation very quickly.     

A Versatile Naphthalimide–Sulfonamide‐Coated Tetraphenylethene: Aggregation‐Induced Emission Behavior,Mechanochromism, and Tracking Glutathione in Living Cells

A tetraphenylethene (TPE) derivative substituted with a sulfonyl‐based naphthalimide unit ( TPE‐Np ) was designed and synthesized. Its optical properties in solution and in the solid state were investigated. Photophysical properties indicated that the target molecule, TPE‐Np , possessed aggregation‐induced emission (AIE) behavior, although the linkage between TPE and the naphthalimide unit was nonconjugated. Additionally, it exhibited an unexpected, highly reversible mechanochromism in the solid state, which was attributed to the change in manner of aggregation between crystalline and amorphous states. On the other hand, a solution of TPE‐Np in a mixture of dimethyl sulfoxide/phosphate‐buffered saline was capable of efficiently distinguishing glutathione (GSH) from cysteine and homocysteine in the presence of cetyltrimethylammonium bromide. Furthermore, the strategy of using poly(ethylene glycol)–polyethylenimine (PEG‐PEI) nanogel as a carrier to cross‐link TPE‐Np to obtain a water‐soluble PEG‐PEI/ TPE‐Np nanoprobe greatly improved the biocompatibility, and this nanoprobe could be successfully applied in the visualization of GSH levels in living cells.     

A 1,3‐Indandione‐Functionalized Tetraphenylethene: Aggregation‐Induced Emission,Solvatochromism, Mechanochromism,and Potential Application as a Multiresponsive Fluorescent Probe

A tetraphenylethene (TPE) derivative substituted with the electron‐acceptor 1,3‐indandione (IND) group was designed and prepared. The targeted IND‐TPE reserves the intrinsic aggregation‐induced emission (AIE) property of the TPE moiety. Meanwhile, owing to the decorated IND moiety, IND‐TPE demonstrates intramolecular charge‐transfer process and pronounced solvatochromic behavior. When the solvent is changed from apolar toluene to highly polar acetonitrile, the emission peak redshifts from 543 to 597 nm. IND‐TPE solid samples show an evident mechanochromic process. Grinding of the as‐prepared powder sample induces a redshift of emission from green (peak at 515 nm) to orange (peak at 570 nm). The mechanochromic process is reversible in multiple grinding–thermal annealing and grinding–solvent‐fuming cycles, and the emission of the solid sample switches between orange (ground) and yellow (thermal/solvent‐fuming‐treated) colors. The mechanochromism is ascribed to the phase transition between amorphous and crystalline states. IND‐TPE undergoes a hydrolysis reaction in basic aqueous solution, thus the red‐orange emission can be quenched by OH^? or other species that can induce the generation of sufficient OH^?. Accordingly, IND‐TPE has been used to discriminatively detect arginine and lysine from other amino acids, due to their basic nature. The experimental data are satisfactory. Moreover, the hydrolyzation product of IND‐TPE is weakly emissive in the resultant mixture but becomes highly blue‐emissive after the illumination for a period by UV light. Thus IND‐TPE can be used as a dual‐responsive fluorescent probe, which may extend the application of TPE‐based molecular probes in chemical and biological categories.     

One‐Pot Three‐Component Synthesis of 2‐Amino Pyrimidines in Aqueous PEG‐400 at Ambient Temperature

Amino pyrimidines have been synthesized by a one‐pot procedure under environmentally friendly reaction conditions at room temperature. The use of aqueous PEG‐400 circumvents the problems associated with the toxic, hazardous organic solvents and oxidizing agents.     

A solution‐processible poly(p‐phenylene vinylene) without alkyl substitution: Introducing the cis‐vinylene segments in polymer chain for improved solubility,blue emission,and high efficiency

A soluble all‐aromatic poly(2,5‐diphenyl‐1,4‐phenylenevinylene) (2,5‐DP‐PPV) is synthesized by utilizing aromatic phosphonium and aldehyde monomers through Wittig reaction. The H¹ NMR and FTIR measurements indicate that over 50% content of cis‐vinylene units exist in polymer backbone. The diphenyl‐substituted benzaldehyde monomer plays an important role to enhance cis‐products (Z‐selectivity) in Wittig reactions. The twisted cis‐segments in polymer backbone reduce the interchain interactions and enhance the solubility of such all‐aromatic PPV derivative in common organic solvents. 2,5‐DP‐PPV exhibits good solubility in common organic solvents, such as tetrahydrofuran and chloroform. The polymer film exhibits a blue light emission (λ_max = 485 nm) and a very high photoluminescence efficiency of 78%. The cis‐trans photo isomerization of this polymer in solution and the impact on the optical properties are also investigated. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5242–5250, 2008     

Thermogelling behaviors of poly(caprolactone‐b‐ethylene glycol‐b‐caprolactone) triblock copolymer in the presence of hyaluronic acid

In this article, we studied the effect of hyaluronic acid (HA) on thermogelation of poly(caprolactone‐b‐ethylene glycol‐b‐caprolactone) (PCL‐PEG‐PCL) aqueous solution designed as an injectable system for prevention of postsurgical tissue adhesion. The PCL‐PEG‐PCL triblock copolymers were simply synthesized by ring‐opening polymerization of ε‐caprolactone (CL) in the presence of PEG as a polymeric initiator. The synthesized copolymers were confirmed by proton nuclear magnetic resonance (¹H‐NMR) spectroscopy. Possible interactions between HA and PCL‐PEG‐PCL triblock copolymers in the blend were evaluated by Fourier‐transform infrared spectroscopy (FTIR). The effect of HA on the micellization of PCL‐PEG‐PCL aqueous solution was investigated by dye solubilization method and electrophoretic lighting scattering (ELS) spectrophotometer. Also, the thermogelling behaviors of the PCL‐PEG‐PCL triblock copolymers in the presence of HA and their mechanism were investigated by test tube inverting method, ¹³C‐NMR, ¹H‐NMR, Advanced Rheometic Expansion System (ARES), and differential scanning calorimetry (DSC). The PCL‐PEG‐PCL/HA blend aqueous solutions undergo the sol‐gel‐sol transition in response to an increase in temperature (10–60 °C) and the gelation of the PCL‐PEG‐PCL was rather accelerated by HA. Presumably, this accelerated gelation seems to arise from the attractive interactions between them and the effect of chain confinement in the micelle corona region. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3629–3637, 2008     

Synthesis of thermal‐stable and photo‐crosslinkable polyfluorenes for the applications of polymer light‐emitting diodes

Three polyfluorene derivatives which have oxetane‐containing phenyl group at C‐9 position were synthesized via the palladium‐catalyzed Suzuki‐coupling reaction. The synthesized polymers PFB, PFG, and PFR emit blue, green, and red light, respectively. A double‐layer device with the configuration of ITO/PEDOT/polymer/Ca/Al using PFB as the active layer showed a threshold voltage of 5 V, a maximum brightness of 2030 cd/m², and a maximum current efficiency of 0.35 cd/A. Using PFG as the active layer, the device exhibited a threshold voltage of 6 V, a maximum brightness of 6447 cd/m², and a maximum current efficiency of 1.27 cd/A. Using PFR as the active layer, the device showed a threshold voltage of 4 V, a maximum brightness of 2135 cd/m², and a maximum current efficiency of 0.16 cd/A. Better electroluminescent performance was also found based on different design of device structures. Due to photo‐crosslinking property of oxetane groups, the UV‐exposed thin films are insoluble in common organic solvents. A device comprised of blue, green, and red‐emissive pixels was successfully fabricated by spin‐coating and photo‐lithographic processes. In addition, a white light‐emitting device with CIE coordinate of (0.34, 0.33) was achieved by blending PFR into a host material PFB as the active layer. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 516–524, 2010     

Microencapsulation of protein‐loaded polysaccharide particles within poly(D,L‐lactic‐co‐glycolic acid) microspheres using S/O/W: characterization and release studies

This report demonstrates a process to form polysaccharide glassy particles without water–oil or water–air interfaces as well as ionic polymers and its application in formulating sustained‐release dosage forms for structurally delicate proteins. When a co‐solution containing dextran and polyethylene glycol (PEG) was subjected to freeze‐drying, the dextran separated out of the solution to form dispersed phases surrounded by a PEG‐rich continuous phase and was solidified during subsequent lyophilization to fine glassy particles, 1–2 µm in diameter. Water‐soluble proteins can easily be loaded in these glassy particles due to preferential partition and become resistant to organic solvents simply by adding them into the dextran‐PEG co‐solution. After washing away the PEG continuous phase with organic solvents, the protein‐containing glassy particles can be suspended in a hydrophobic polymer solution and formulated into various pharmaceutical dosage forms and medical devices for sustained‐release protein delivery. In the present study, myoglobin, bovine serum albumin (BSA), and β‐galactosidase (β‐gal) were formulated in PLGA mcirospheres and as model proteins using this glassy particulate approach, and subjected to a series of assays for release kinetics, structural integrity, and bioactivity. The experimental results indicated that this system offered well preserved protein integrity and bioactivity as well as significantly improved protein release kinetics. Copyright © 2008 John Wiley & Sons, Ltd.     

Diels–Alder Polymer Networks with Temperature‐Reversible Cross‐Linking‐Induced Emission

A novel synthetic strategy gives reversible cross‐linked polymeric materials with tunable fluorescence properties. Dimaleimide‐substituted tetraphenylethene (TPE‐2MI), which is non‐emissive owing to the photo‐induced electron transfer (PET) between maleimide (MI) and tetraphenylethene (TPE) groups, was used to cross‐link random copolymers of methyl (MM), decyl (DM) or lauryl (LM) methacrylate with furfuryl methacrylate (FM). The mixture of copolymer and TPE‐2MI in DMF showed reversible fluorescence with “on/off” behavior depending on the Diels–Alder (DA)/retro‐DA process, which is easily adjusted by temperature. At high temperatures, the retro‐DA reaction is dominant, and the fluorescence is quenched by the photo‐induced electron transfer (PET) mechanism. In contrast, at low temperatures, the emission recovers as the DA reaction takes over. A transparent PMFM/TPE‐2MI polymer film was prepared which shows an accurate response to the external temperature and exhibited tunable fluorescent “turn on/off” behavior. These results suggest the possible application in areas including information security and transmission. An example of invisible/visible writing is given.     

Organic Nanoprobes for Fluorescence and 19F Magnetic Resonance Dual‐Modality Imaging

Multimodal imaging techniques have been demonstrated to be greatly advantageous in achieving accurate diagnosis and gained increasing attention in recent decades. Herein, we present a new strategy to integrate the complementary modalities of ¹⁹F magnetic resonance imaging (¹⁹F MRI) and fluorescence imaging (FI) into a polymer nanoprobe composed of hydrophobic fluorescent organic core and hydrophilic fluorinated polymer shell. The alkyne‐terminated fluorinated copolymer (Pn) of 2,2,2‐trifluoroethyl acrylate (TFEA) and poly(ethylene glycol) methyl ether acrylate (PEGA) was first prepared via atom transfer radical polymerization (ATRP). The PEGA plays an important role in both improving ¹⁹F signal and modulating the hydrophilicity of Pn. The alkynyl tail in Pn is readily conjugated with azide modified tetra‐phenylethylene (TPE) through click chemistry to form azo polymer (TPE‐azo‐Pn). The core‐shell nanoprobes (TPE‐P3N) with an average particle size of 57.2 ± 8.8 nm are obtained via self‐assembly with ultrasonication in aqueous solution. These nanoprobes demonstrate high water stability, good biocompatibility, strong fluorescence and good ¹⁹F MRI performance, which present great potentials for simultaneous fluorescence imaging and ¹⁹F–MR imaging.     

Macromolecular Organization of Poly(L‐lactide)‐block‐Polyoxyethylene into Bio‐Inspired Nano‐Architectures

Block copolymers create various types of nano‐structures, e. g., spheres, rods, cubes, and lamellae. This review discloses the dynamic macromolecular organization of block copolymers comprising poly(L ‐lactide) (PLLA) and poly(oxyethylene) (PEG) that allows to simulate elaborate biological systems. The block copolymers, AB‐ (PLLA‐PEG) and ABA‐type (PLLA‐PEG‐PLLA), are synthesized by ordinary lactide polymerization to have a controlled block length. They are dispersed into an aqueous medium to prepare nano‐scale particles, consisting of hydrophobic PLLA and hydrophilic PEG in the core and shell, respectively. Then, the particles are placed on a flat substrate by the casting method. The particles are detected as discoids by AFM, having shrunk with loss of water. Heat‐treatment of these particles at 60°C (above T_g of PLLA) gives rise to a collapse into small fragments, which then aggregate into bands with nano‐size width and thickness. The PLLA‐PEG bands align parallel to each other, while the PLLA‐PEG‐PLLA bands form a characteristic network resembling the neuron system created in animal tissue. As analyzed by TEM diffraction, each is composed of α‐crystal of PLLA whose c‐axis (molecular axis) is perpendicular to the substrate surface. Based on this fact, a doubly twisted chain structure of PLLA is proposed in addition to a plausible mechanism for the self‐organization of the block copolymers. Derivatives of the PLLA‐PEG block copolymers can form far more interesting nano‐architectures. An equimolar mixture of enantiomeric copolymers, PLLA‐PEG‐PLLA and PDLA‐PEG‐PDLA, forms a hydrogel that is thermo‐responsive. The terminal‐modified poly(L ‐lactide)‐block‐polyoxyethylene monocinnamate (PLLA‐PEG‐C) forms a highly stabilized nanofiber by the photo‐reaction of the cinnamates placed in the outer layer of the nanobands.     

Highly redox‐stable and electrochromic aramids with morpholinyl‐substituted triphenylamine units

A novel morpholinyl‐substituted, triphenylamine‐based diamine monomer, namely 4,4′‐diamino‐4″‐(4‐morpholinyl)triphenylamine, was synthesized and polymerized with various aromatic dicarboxylic acids via the phosphorylation polyamidation reaction leading to a series of electroactive aromatic polyamides (aramids). All aramids were readily soluble in polar organic solvents and could be solution cast into tough and flexible films with high thermal stability. Cyclic voltammograms of the aramid films on the indium‐tin oxide‐coated glass substrate exhibited a pair of reversible oxidation waves with very low onset potentials of 0.36 − 0.41 V (vs. Ag/AgCl) in acetonitrile solution. The polymer films showed reversible electrochemical oxidation accompanied by strong color changes with high coloration efficiency, high contrast ratio, and rapid switching time. The optical transmittance change (Δ%T) at 650 nm between the neutral state and the fully oxidized state is up to 90%. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1289–1298     

CO2‐ and O2‐Sensitive Fluorophenyl End‐Capped Poly(ethylene glycol)

Pentafluorophenyl end‐capped poly(ethylene glycol) (PF‐PEG‐PF) aqueous solution shows a lower critical solution temperature (LCST), which is sensitive to the type of gases dissolved in the solution. LCST increases from 24.5 to 26 °C when dissolved carbon dioxide is replaced by oxygen. The transparent‐to‐turbid transition is reversibly observed when the dissolved carbon dioxide in the PF‐PEG‐PF aqueous solution is exchanged with oxygen, and vice versa, at 24.5 °C. ¹⁹F NMR and ¹H NMR spectra of the PF‐PEG‐PF in D₂O suggest that 1) dehydration of PEG is the main reason of developing LCST of the PF‐PEG‐PF aqueous solution, 2) minute differences in the intermolecular interactions, as demonstrated by changes in the chemical shift of the PF‐PEG‐PF peaks, induce such a difference in LCST. This paper provides a new insight in designing a stimuli‐responsive polymer in that fine tuning of a phase transition can be controlled by the type of dissolved gas.

     

A Photo‐Triggered Traceless Staudinger–Bertozzi Ligation Reaction

The use of light to control the course of a chemical/biochemical reaction is an attractive idea because of its ease of administration with high precision and fine spatial resolution. Staudinger ligation is one of the commonly adopted conjugation processes that involve a spontaneous reaction between azides and arylphosphines to form iminophosphoranes, which further hydrolyze to give stable amides. We designed an anthracenylmethyl diphenylphosphinothioester ( 1 ) that showed promising Staudinger ligation reactivity upon photo‐excitation. Broadband photolysis at 360–400 nm in aqueous organic solvents induced heterolytic cleavage of its anthracenylmethyl–phosphorus bond, releasing a diphenylphosphinothioester ( 2 ) as an efficient traceless Staudinger–Bertozzi ligation reagent. The quantum yield of such a photo‐induced heterolytic bond‐cleavage at the optimal wavelength of photolysis (376 nm) at room temperature is ≥0.07. This work demonstrated the feasibility of photocaging arylphosphines to realize the photo‐triggering of the Staudinger ligation reaction.     

Porphyrin/Platinum(II) C^N^N Acetylide Complexes: Synthesis,Photophysical Properties,and Singlet Oxygen Generation

A new class of substituted porphyrins has been developed in which a different number of cyclometalated Pt^II C^N^N acetylides and polyethylene glycol (PEG) chains are attached to the meso positions of the porphyrin core, which are meant for photophysical, electrochemical, and in vitro light‐induced singlet oxygen (¹O₂) generation studies. All of these Zn^II porphyrin–Pt^II C^N^N acetylide conjugates show moderate to high (Φ_Δ=0.55 to 0.63) singlet oxygen generation efficiency. The complexes are soluble in organic solvents but, despite the PEG substituents, slowly aggregate in aqueous solvent systems. These conjugates also exhibit interesting photophysical properties, including near‐complete photoinduced energy transfer (PEnT) through the rigid acetylenic bond(s) from the Pt^II C^N^N antenna units to the Zn^II porphyrin core, which shows sensitized luminescence, as shown by quenching of Pt^II C^N^N‐based luminescence. Electrochemical measurements show a set of redox processes that are approximately the sum of what is observed for the Pt^II C^N^N acetylide and Zn^II porphyrin units. UV/Vis spectroscopic properties are supported by DFT calculations.