Research data supporting "Methacrylate-based copolymers as tunable hosts for triplet-triplet annihilation upconversion"

1H and 13C nuclear magnetic resonance spectra were recorded on a Bruker Avance III 400 or Magritek Spinsolve 60 spectrometer at 293 K. Chemical shifts are reported as δ in parts per million (ppm) and referenced to the chemical shift of the residual solvent resonances (CDCl3: 1H: δ = 7.26 ppm, 13C: δ = 77.16 ppm). Polymer molecular weight and dispersity were determined using a Malvern Viscotek GPCmax size exclusion chromatograph instrument fitted with a Viscotek TDA 305 detector unit equipped with refractive index and light scattering detectors. Samples were dissolved in tetrahydrofuran at a concentration of approximately 1 mg mL-1 and eluted through a guard column and two Agilent PLGel 5 µm mixed C columns (300 x 7.5 mm) at a flow rate of 1 ml.min-1; the elution pathlength was heated to 30 °C for the duration. Molecular weights were calibrated against known poly(methyl acrylate) standards. Differential scanning calorimetry was conducted using a TA Instruments Discovery 2500. Samples were analysed in non-hermetic aluminium pans and compared against an empty reference pan of the same type. Loaded sample masses were between 3 and 10 mg. Samples were subjected to two complete heat/cool cycles from -50 °C to 150 °C (-85 °C to 150 °C for lower Tg samples) and both heating and cooling rates were set at 10 °C min-1. UV/Vis transmittance and absorption spectra were measured with a PerkinElmer Lambda 750 spectrophotometer. Transmittance spectra of films were measured using wavelength scan with a resolution of 1 nm at a scan speed of 267 nm/min and a slit width of 2 nm. Samples were directly mounted to the sample holder. Solution spectroscopy was carried out on solutions in THF in quartz SUPRASIL® cuvettes (10 mm pathlength). Absorption spectra of luminophore solutions were taken using a wavelength scan with a resolution of 0.5 nm at a scan speed of 141.20 nm/min and a slit width of 2 nm. A reference sample of THF in an identical cuvette was used to apply a 100% transmission correction. Steady-state PL spectroscopy was performed on a Fluorolog-3 spectrophotometer (Horiba Jobin Yvon). Solid-state emission spectra were recorded using the front-face configuration. Solution emission spectra were recorded using the right-angle configuration, over 10 averaged scans. The excitation and emission slits were adjusted so that the maximum PL intensity was within the range of linear response of the detector and were kept the same between samples if direct comparison between the emission intensity was required. Emission and excitation spectra were corrected for the wavelength response of the system and the intensity of the lamp profile over the excitation range, respectively, using correction factors supplied by the manufacturer. Photoluminescence quantum yields (ΦPL) were measured using a Quanta-phi integrating sphere (Horiba Jobin Yvon) mounted on the Fluorolog-3 spectrophotometer. The UC emission and phosphorescence spectra, threshold intensity (I_th), UC quantum yield (UC) and lifetime measurements were performed using an FLS1000 time-correlated single photon counting (TCSPC) spectrometer (Edinburgh Instruments Ltd.). The samples were excited with a 532 nm laser (MGL-III-532, 200mW). To determine I_th, the laser power was adjusted using a Thorlabs PM100A Power Meter Console combined with a S120VC Si photodiode power sensor (range: 200-1100 nm) before the measurement, across the 5 to 8000 mW cm-2. The ΦUC was measured with an integrating sphere (SNS125 5-inch sphere, three windows, International Light Technologies). The sample was placed at the center of the sphere using a sample holder. A baffle is placed in front of the observation window, which blocks any scattering and reflection of the laser from the sample surface. The angle of the sample holder is adjustable. The normal direction of the sample holder is 22.5˚ to the excitation beam line, which leads the reflection of the laser to the inner surface of the sphere. The laser power was measured with a photodiode before each ΦUC measurement. Both the emission of the sample (380-500 nm) and scattering of the laser beam (530-534 nm) were measured. A neutral density filter (O.D.=3.0) was placed before the excitation beam for the scattering intensity measurements. Six data sets were collected to calculate the ΦUC of each sample: 1. sample in the path of the beam – “in fluorescence”; 2. sample in scattering; 3. sample facing away from beam – “out of fluorescence”, 4. sample out of scattering; 5. empty sphere fluorescence; 6. empty sphere scattering. Fluorescence decay measurements were performed using the multi-channel scaling (MCS) method on a the FLS1000 TCSPC spectrometer. The emission decay was recorded using a photomultiplier tube (PMT-980) equipped with TCC2 counting electronics. For the upconversion lifetime measurements, a wavelength of 440 nm was selected, and a short-pass filter (cut-off at 500 nm, Thorlabs) was placed in front of the detector. For the phosphorescence lifetimes, a wavelength of 660 nm was selected, and a long-pass filter (cut-off 550 nm, Thorlabs) was used. The instrument response function (IRF) was measured using Ludox® colloidal silica solution (a SiO2 particle suspension solution) and using a neutral density filter (O.D.=3) to attenuate the laser intensity. The pulse repetition rate was adjusted to ensure the full decay was detected within the time window. Data-fitting was carried out by tail fitting to each emission decay trace using a multiexponential decay function within the FAST software package (Edinburgh Instruments Ltd.). The goodness of fit was evaluated using the reduced chi-square statistics (χ2) and the randomness of the residuals. Please also see the readme file for more details on data collection and file organisation.

1H与13C核磁共振（nuclear magnetic resonance, NMR）谱于293 K下，在布鲁克（Bruker）Avance III 400型或Magritek Spinsolve 60型光谱仪上采集。化学位移以δ值（单位：百万分之一，ppm）报告，并以残留溶剂峰的化学位移为参照基准（氘代氯仿CDCl3：¹H NMR δ=7.26 ppm，¹³C NMR δ=77.16 ppm）。聚合物分子量与分散度采用配备Viscotek TDA 305检测器单元（集成示差折光检测器与光散射检测器）的马尔文（Malvern）Viscotek GPCmax尺寸排阻色谱仪测定。样品以约1 mg·mL⁻¹的浓度溶解于四氢呋喃（tetrahydrofuran, THF）中，经保护柱与两根安捷伦（Agilent）PLGel 5 µm混合型C色谱柱（300 × 7.5 mm）洗脱，洗脱流速为1 mL·min⁻¹，洗脱过程中柱温维持于30 ℃。分子量校准采用已知的聚丙烯酸甲酯（poly(methyl acrylate)）标准品完成。差示扫描量热法（differential scanning calorimetry, DSC）测试使用TA仪器公司Discovery 2500型差示扫描量热仪。样品置于非密封铝坩埚中，以同类型空坩埚作为参比。样品装载量为3~10 mg。样品经历两次完整的升降温循环：温度范围为-50 ℃至150 ℃（低玻璃化转变温度样品则采用-85 ℃至150 ℃），升降温速率均设为10 ℃·min⁻¹。紫外-可见光透过率与吸收光谱采用珀金埃尔默（PerkinElmer）Lambda 750型分光光度计测定。薄膜样品的透过光谱以波长扫描模式采集，扫描分辨率为1 nm，扫描速度为267 nm·min⁻¹，狭缝宽度为2 nm，样品直接固定于样品架上。溶液光谱测试采用光程为10 mm的石英SUPRASIL®比色皿，以THF为溶剂。发光体溶液的吸收光谱以波长扫描模式采集，扫描分辨率为0.5 nm，扫描速度为141.20 nm·min⁻¹，狭缝宽度为2 nm；以同型号比色皿中的纯THF溶液作为参比，进行100%透过率校正。稳态光致发光（photoluminescence, PL）光谱测试采用Horiba Jobin Yvon公司的Fluorolog-3型分光光度计。固态发射光谱采用正面照射配置采集，溶液发射光谱采用直角照射配置采集，平均扫描次数为10次。激发与发射狭缝宽度调节至使最大PL强度处于检测器线性响应区间内；若需直接比较发射强度，样品间狭缝参数保持一致。发射光谱与激发光谱分别通过仪器厂商提供的校正因子，针对系统波长响应与激发范围内的灯谱分布进行了强度校正。光致发光量子产率（ΦPL）采用安装于Fluorolog-3分光光度计上的Horiba Jobin Yvon公司Quanta-phi积分球测定。上转换（upconversion, UC）发射光谱、磷光光谱、阈值强度（I_th）、上转换量子产率（ΦUC）以及寿命测试均采用爱丁堡仪器有限公司（Edinburgh Instruments Ltd.）的FLS1000型时间相关单光子计数（time-correlated single photon counting, TCSPC）分光光度计完成。样品由532 nm激光器（MGL-III-532，200 mW）激发。阈值强度I_th的测定前，采用Thorlabs PM100A型功率计控制台搭配S120VC型硅光电二极管功率传感器（量程：200~1100 nm）校准激光功率，校准范围为5~8000 mW·cm⁻²。上转换量子产率ΦUC采用International Light Technologies公司的SNS125型5英寸三窗口积分球测定。样品放置于积分球中心的样品支架上，观测窗口前加装挡板以阻挡样品表面散射或反射的激光。样品支架法线与激发光束夹角为22.5°，可将激光反射至积分球内表面。每次ΦUC测试前均采用光电二极管测定激光功率。测试涵盖样品发射（380~500 nm）与激光散射（530~534 nm）两个波段：散射强度测试时，在激发光路前加装光密度（O.D.）=3.0的中性密度滤光片。每个样品的ΦUC计算需采集6组数据集：1. 光束路径内的样品——“荧光开启”状态；2. 样品散射状态；3. 光束背离方向的样品——“荧光关闭”状态；4. 样品无散射状态；5. 空积分球的荧光本底；6. 空积分球的散射本底。荧光寿命测试采用FLS1000 TCSPC分光光度计的多通道缩放（multi-channel scaling, MCS）方法完成，发射寿命通过搭载TCC2计数电子学组件的光电倍增管（PMT-980）采集。上转换寿命测试选取440 nm激发波长，并在检测器前加装截止波长为500 nm的Thorlabs短通滤光片；磷光寿命测试选取660 nm激发波长，并使用截止波长为550 nm的Thorlabs长通滤光片。仪器响应函数（instrument response function, IRF）采用Ludox®胶体二氧化硅溶液（SiO₂颗粒悬浮液），搭配O.D.=3的中性密度滤光片衰减激光强度进行测定。调整脉冲重复频率以确保完整的衰减信号可被时间窗口内采集。数据拟合采用爱丁堡仪器有限公司FAST软件包中的多指数衰减函数，对每条发射衰减曲线进行尾部拟合；拟合优度通过简化卡方统计量（χ²）与残差的随机性进行评估。更多数据采集与文件组织结构的细节请参见README文件。