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Abstract The interface between the hole transport layer (HTL) and perovskite in p‐i‐n perovskite solar cells (PSCs) plays a vital role in the device performance and stability. However, the impact of this interface on the vertical phase segregation of mixed halide perovskite remains insufficiently understood. This work systematically investigates the impact of chemical and electronic properties of HTL on vertical halide segregation of mixed‐halide perovskites. This work shows that incorporating a poly[bis(4‐phenyl) (2,4,6‐trimethylphenyl) amine] (PTAA)/CuI_xBr_1‐xbilayer as the HTL significantly suppresses light‐induced vertical phase segregation in MAPb(I_0.7Br_0.3)₃. This work uses grazing‐incidence X‐ray diffraction (GIXRD) to capture the depth‐resolved composition change of MAPb(I_0.7Br_0.3)₃at the interface and within the bulk under illumination. By changing the illumination direction and the electronic properties of HTL, this work elucidates the roles of charge carrier extraction and interfacial defects on vertical phase segregation. The PTAA/CuI_xBr_1‐xbilayer, with its synergistic passivation and efficient hole extraction ability, stabilizes the interface and bulk of the mixed halide perovskite layer and prevents phase segregation. This work underscores that synergetic passivation and efficient hole extraction pack a more powerful punch for arresting the vertical phase segregation in mixed‐halide perovskite. 

Magnetic fields offer a powerful means to control molecular emission, enabling quantum sensing and spin-level control of chemical reactions. Here, we demonstrate a strategy to magnetically control red to near-infrared phosphorescence via triplet–triplet energy transfer (TTET) from donor–chiral bridge–acceptor (D−χ–A) molecules that generate spin-correlated radical pairs (SCRPs) upon photoexcitation. These SCRPs yield non-emissive triplet excited states whose formation is sensitive to magnetic fields. By transferring this energy to emissive Pt- and Pd-based π-extended porphyrins, we enable magnetic control over phosphorescence that would otherwise be unresponsive to weak magnetic fields (<1 T). This approach establishes a platform for quantifying magnetic field effects on silent triplet states while extending magnetically responsive emission into the near-infrared. Coupling SCRP-based molecular magnetic switches to long-wavelength emissive acceptors offers a new way for probing and modulating spin-dependent processes and triplet-state populations in molecular systems. 

Spin chemistry of photogenerated spin-correlated radical pairs (SCRPs) offers a practical approach to control chemical reactions and molecular emissions by using weak magnetic fields. This capability to harness magnetic field effects (MFEs) paves the way for developing SCRPs-based molecular qubits. Here, we introduce a new series of donor–chiral bridge–acceptor (D−χ–A) molecules that demonstrate significant MFEs on fluorescence intensity and lifetime in solution at room temperature─critical for quantum sensing. By precisely tuning the donor site through torsional locking, distance extension, and planarization, we achieved remarkable control over key quantum properties, including field-response range and line width. In the most responsive systems, emission lifetimes increased by over 200%, and the total emission intensity was modulated by up to 30%. This level of tunability shows the power of synthetic spin chemistry. The rational design principle of optically addressable SCRP-based molecular systems, presented in this work, represents a major leap toward functional synthetic molecular qubits, advancing the field of molecular quantum technologies. 

Triplet–triplet annihilation (TTA) enables photon upconversion by combining two lower-energy triplet excitons to produce a higher-energy singlet exciton. This mechanism enhances light-harvesting efficiency for solar energy conversion and enables the use of lower-energy photons in bioimaging and photoredox catalysis applications. The magnetic modulation of such high-energy excitons presents an exciting opportunity to develop molecular quantum information technologies. While the spin dynamics of triplet exciton pairs are sensitive to external magnetic fields, the magnetic field effects (MFEs) associated with these pairs are generally limited by spin statistics to at most 10% at low fields (<1 T), making them challenging to apply in technological advancements. In contrast, MFEs on spin-correlated radical pairs (SCRPs) can be significantly greater, surpassing those on triplet pairs. By using SCRPs-based molecular qubits as triplet sensitizers in the sensitized TTA scheme, we can magnetically modulate TTA and consequently, the delayed fluorescence of annihilators. In our current system, we have achieved more than 70% magnetic modulation of delayed fluorescence, effectively harnessing and even amplifying magnetic modulation within SCRPs to influence high-energy excitons. This work opens new opportunities for advancing spin-controlled chemical reactions and molecular quantum information technologies. 

Spin chemistry of photogenerated spin-correlated radical pairs (SCRPs) offers a practical approach to control chemical reactions and molecular emissions using weak magnetic fields. This capability to harness magnetic field effects (MFEs) paves the way for developing SCRPs-based molecular qubits. Here, we introduce a new series of donor-chiral bridge-acceptor (D-χ-A) molecules that demonstrate significant MFEs on fluorescence intensity and lifetime in solution at room temperature – critical for quantum sensing. By precisely tuning the donor site through torsional locking, distance extension, and planarization, we achieved remarkable control over key quantum properties, including field-response range and linewidth. In the most responsive systems, emission lifetimes increased by over 200%, and total emission intensity was modulated by up to 30%. This level of tunability, and rational design principle of optically addressable molecular qubits, represents a major leap toward functional synthetic molecular qubits, advancing the field of molecular quantum technologies. 

The degree of torsional hindrance can significantly contribute to anti-Arrhenius behavior of charge recombination, wherein recombination rates decrease as temperature increases.