Open Access Article
Konstantinos T.
Kotoulas
abc,
Thomas
Hinton
a,
Ethan
Macallister
a,
Jai
Ram
a,
John D.
Wallis
c,
Yunhong
Jiang
d,
Andrew D.
Burrows
b,
Gareth W. V.
Cave
d and
Ming
Xie
*a
aDepartment of Chemical Engineering, University of Bath, Bath, BA2 7AY, UK. E-mail: m.xie2@bath.ac.uk
bDepartment of Chemistry, University of Bath, Bath BA2 7AY, UK
cSchool of Science and Technology, Nottingham Trent University, Nottingham, NG11 8NS, UK
dDepartment of Applied Sciences, Northumbria University, Newcastle NE1 8ST, UK
First published on 10th April 2026
Improving crop productivity without increasing land, energy or chemical inputs is a critical challenge for sustainable agriculture, and spectral conversion materials that transform underutilized ultraviolet radiation into photosynthetically active radiation (PAR) offer a promising solution. Here, we report copper-based luminescent composites that enable wavelength-selective spectral reshaping and evaluate their physiological impact on Raphanus sativus grown under controlled greenhouse conditions. Three complementary materials were developed: melt-quenched glass composites incorporating the copper iodide clusters [Cu4I4(PPh3)4] and [Cu4I4(PPh2Et)4], and flexible cellulose acetate films embedded with copper-carbon nanoassemblies (Cu-CNAs), producing blue-green, yellow, and blue emissions, respectively, within the PAR window. Plant trials revealed clear wavelength dependent responses, with blue and blue-green emission accelerating early foliar expansion, while prolonged exposure to the yellow emitting [Cu4I4(PPh2Et)4] composite delivered the highest final biomass and significantly increased chlorophyll, carotenoid and ascorbic acid content, indicative of enhanced carbon assimilation and photoprotective metabolism. These results demonstrate that copper-based luminescent composites provide a scalable, low-cost and sustainable platform for spectral optimization in controlled environment agriculture, offering a practical materials driven strategy to improve both crop yield and nutritional quality.
Sustainability spotlightThis work advances sustainable agriculture by enabling yield and nutritional gains without increasing land use, fertiliser inputs, or energy demand. Copper-based luminescent composites convert underutilised and potentially harmful UV radiation into photosynthetically active wavelengths, improving photosynthetic efficiency, biomass accumulation, and micronutrient content under controlled growth conditions. The materials are low-cost, scalable, and based on earth-abundant copper, offering a lower environmental footprint than rare-earth or precious-metal phosphors. By enhancing crop productivity through passive spectral optimisation, this research supports SDG 2 (Zero Hunger), SDG 12 (Responsible Consumption and Production), and SDG 13 (Climate Action), contributing to resilient, resource-efficient food production systems. |
Photosynthetically active radiation (PAR; 400–700 nm) is the range of light most efficiently absorbed by chlorophylls and carotenoids for driving photosynthesis.2 However, a significant fraction of incoming solar radiation lies outside this range, particularly in the ultraviolet (UV) region, which can be photodamaging and is poorly utilized by plants.3,4 Materials that harvest UV light and convert it into red, blue, or green light can enhance the photon flux in spectral regions most relevant to photosynthesis, thereby improving photosynthetic efficiency.
Red light (650–700 nm) is particularly efficient in stimulating CO2 fixation,5,6 while blue light (450–490 nm) supports chlorophyll biosynthesis and photomorphogenic development through cryptochrome activation.7,8 Green light, once considered inefficient, has been shown to penetrate deeper into leaf mesophyll layers, promoting photosynthesis in tissues not reached by red or blue light, improving drought tolerance and growth rate.9,10 A balanced spectral profile incorporating all three wavelengths is essential for optimal plant development and avoiding phenomena such as “red light syndrome”, which can reduce pigment production and leaf health when plants are grown under monochromatic red light alone.2
Copper nanoclusters (Cu-NCs) and copper halide-based materials offer a sustainable and tuneable approach to spectral conversion.11 Cu-NCs exhibiting strong photoluminescence, are water-soluble, less toxic and more economical to produce, with a lower environmental impact than alternative precious metal nanoparticle (Au, Ag) approaches and or lanthanide-based phosphors.12,13 In addition, these materials can be integrated into polymeric films (e.g. cellulose acetate) or immobilized within inorganic glass matrices to create luminescent coatings and filters that convert UV radiation into PAR wavelengths.
In this study, we detail the development of copper-based fluorescent composites, including melt-quenched copper phosphine halide complexes and polymer films containing Cu-NCs that convert harmful UV radiation into beneficial yellow, blue, or green light. These materials are designed for integration into greenhouse environments or as leaf-adjacent films to modulate the incoming light spectrum and enhance photosynthetic performance.
000), copper(I) iodide (98.0%), polyvinylpyrrolidone (PVP, 99.0%), potassium phosphate (99.0%), diethyl ether (Et2O, 97.5%), triphenylphosphine (PPh3, 98.5%), phosphoric acid (H3PO4, 85.0%), potassium chloride (KCl, 99.0%), potassium hydroxide (KOH, 85.0%), sodium phosphate dibasic (99.0%), triethyl amine (TEA, 99.5%), ethyl acetate (EtOAc, 99.5%), and sodium phosphate monobasic (99.0%) were all purchased from Sigma-Aldrich. Chloroform (99.8%), ethanol (EtOH, 99.0%) and hydrochloric acid (HCl, 37.0, were obtained from Fisher Scientific UK. Acetone (99.0%) and methanol (MeOH, 99.5%) were sourced from VWR Chemicals. All aqueous solutions were prepared using distilled water from an ELGA PURELAB Option-S 15BP benchtop water purification system (18.2 MΩ cm).
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1. X-ray diffraction data were collected on a Rigaku XtaLAB Synergy-DW diffractometer using MoKα radiation at 140 K for the ethyldiphenylphosphine complex, and CuKα radiation at 120 K for the triphenylphosphine complex. The structures were solved with SHELXT,15 and refined with SHELXL,16 using the OLEX2 program.17 Illustrations were made with MERCURY.18
Throughout the trials, plant foliage area was monitored at different stages of the trial and quantified using ImageJ software. Post harvest, the crops were weighed and then lyophilized, under a vacuum (<5 Pa) at a condenser temperature of −71.8 °C.
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25) and agitated under dark conditions (room temperature for 24 h). The phosphate buffer (1 L) consisted of 25 mL of 1 M KOH (25 mL, 1 M),1 M phosphoric acid (30 mL, 1 M), and methanol (100 mL, HPLC grade). After 24 h, the mixture was centrifuged (7000 rpm, 10 minutes) using an Eppendorf 5418 R centrifuge, and the aqueous phase was collected and filtered through a syringe filter (0.22 µm). Ascorbic acid content was quantified using an Agilent 1290 Infinity II HPLC system with a diode-array detector (DAD). Separation was performed on a Restek Raptor C18 column (2.7 µm particle size, 100 mm length, 4.6 mm diameter), using phosphate buffer as the mobile phase (0.3 mL min−1 flow rate, 2 µL injection volume). Detection was monitored at 210 and 265 nm.
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1 v/v) and incubated in the dark (room temperature, 24 h). Following extraction, the supernatant (0.1 mL) was transferred into a Hellma Analytics quartz cuvette (1 cm path length) and diluted to a final volume of 3 mL with the same solvent mixture.
Absorbance measurements were recorded at 440, 645, and 663 nm using an Agilent Cary 60 UV-vis spectrophotometer to quantify the concentrations of chlorophyll a, chlorophyll b, and total carotenoids (SI eqn (S1)–(S4)).
The two copper iodide complexes were melt quenched, to produce fluorescent coatings that were then applied to polymethyl methacrylate planes for greenhouse applications, yielding blue and yellow fluorescence under 365 nm excitation for [Cu4I4(PPh3)4] and [Cu4I4(PPh2Et)4] respectively (Fig. 1). The emission characteristics of the melt-quenched glass composites were assigned based on the structural match between our SCXRD data and the previously reported clusters by Dong et al. (1). Specifically, the [Cu4I4(PPh2Et)4] tetragonal polymorph exhibits a known yellow emission maximum at 585 nm, while the monoclinic [Cu4I4(PPh3)4] exhibits a peak at 570 nm. These values are consistent with the yellow and blue-green fluorescence observed under 365 nm excitation in this study (Fig. 1).
The successful incorporation of copper nanoclusters onto the cellulose acetate film was validated through electron microscopy and spectroscopy. SEM imaging confirmed the formation of granular structures across the polymer surface, distinct from the smoother film and trapped solvent blisters (acetone). Critically, EDX analysis targeted these structures and confirmed they were composed of copper, providing definitive evidence of their successful incorporation. The lack of uniform coating however across the film surface is due to the poor acetone solubility of Cu-PVP, which leads to aggregation of the nanoclusters on the film surface upon solvent casting (Fig. 2). The nanocluster aggregation did not hinder the solid-state fluorescence, but in future trials, nanoclusters with improved acetone solubility should be developed to aid their incorporation in the polymeric film.
[Cu4I4(PPh3)4] and [Cu4I4(PPh2Et)4] complexes embedded in melt-quenched glass and Cu-CNAs in cellulose acetate films (CAF) enables UV-to-visible light conversion (SI Fig. 1). Upon excitation at 365 nm, these materials emit strongly at 585 nm (yellow), 570 nm (green) and 410 nm (blue) respectively, wavelengths that align well with the photosynthetically active radiation (PAR) range (SI Fig. 4). These emissions are expected to supplement underutilized portions of the solar spectrum, particularly in greenhouse environments, increasing photon flux in the red and green regions where chlorophyll absorption and light penetration through leaf tissues are most effective. This UV-conversion strategy reduces photodamage while enhancing internal light availability for deeper chloroplast layers, particularly benefiting C3 crops such as Raphanus sativus.
Post harvest, all treatments resulted in increases to harvestable yield. The [Cu4I4(PPh2Et)4], [Cu4I4(PPh3)4] and CAF treatments increased dry foliar mass by 19%, 19% and 10% respectively. Furthermore, the [Cu4I4(PPh2Et)4] film produced the only treatment to yield a statistically significant increase (56%) in radish average dry mass (1.91 ± 0.77 g), whilst, [Cu4I4(PPh3)4] and CAF treatments also displayed increases of 58% (1.93 ± 1.42 g) and 60% (1.96 ± 1.05 g) respectively compared to the control (1.22 ± 0.32 g). The usage of the [Cu4I4(PPh2Et)4] composite also produced the largest increases in chlorophyll, carotenoids and ascorbic acid content compared to the control, however these did not reach the threshold for statistical significance (p > 0.05) (Table 1). The yellow emission of [Cu4I4(PPh2Et)4] (585 nm, λex 355 nm) overlaps with the broader absorption spectra of chlorophylls and accessory pigments. While this wavelength does not coincide with the primary absorption peaks of chlorophyll a, it aligns with a region of relatively high quantum yield for CO2 assimilation. It is possible that since yellow-green photons can penetrate further into the leaf mesophyll compared to blue or red light (6), photosynthesis can be enhanced in lower chloroplast layers that are typically light-limited, which may enhance the biomass accumulation. The elevated carotenoid content under [Cu4I4(PPh2Et)4] may reflect both increased light harvesting and a demand for photoprotection under higher photosynthetic throughput.23 By contrast, the CAF and PPh3 composites, which shift more energy into blue or blue-green wavelengths, supported chlorophyll accumulation (CAF > control) but did not translate into the same statistically significant for harvestable root biomass as [Cu4I4(PPh2Et)4]. Differences in foliar ascorbic acid between treatments may also be spectrum dependent. The ascorbic acid biosynthesis and turnover are responsive to both high-energy (UV/blue) exposure and overall redox load, so treatments that change the balance of blue vs. red photons, or that fail to supply additional red flux, can plausibly alter ascorbic acid concentration.
| Materials | Average normalised carotenoid (mg L−1) | Average normalised chlorophyll (mg L−1) | Average normalised ascorbic acid (mg L−1) |
|---|---|---|---|
| Control | 2.50 ± 0.07 | 14.5 ± 0.40 | 355 ± 10 |
| [Cu4I4(PPh2Et)4] | 2.84 ± 0.12 | 15.4 ± 0.70 | 363 ± 16 |
| [Cu4I4(PPh3)4] | 2.11 ± 0.11 | 13.1 ± 1.04 | 281 ± 13 |
| CAF | 2.56 ± 0.14 | 14.9 ± 1.03 | 252 ± 19 |
Importantly, the materials reported here combine optical tunability with practical processability. Melt-quenched copper iodide clusters provide robust, inorganic spectral filters, while flexible polymer-based Cu-CNA films offer lightweight and adaptable alternatives suitable for greenhouse integration. The use of earth-abundant copper further strengthens the sustainability and economic viability of this approach relative to precious metal or rare earth phosphors.
Beyond the specific crop examined, these findings establish a generalizable framework for the rational design of spectral conversion materials tailored to plant developmental stage, crop type, and growth environment. Future work should firstly employ pot-level replication across multiple blocks to further validates these spectra effects whilst accounting for environmental variance between containers. Secondly future studies should focus on improving long-term photostability, engineering dual- or broadband-emission systems, and validating performance across diverse crops and real-world greenhouse settings. Taken together, this work positions copper-based luminescent composites as a promising materials platform for enhancing photosynthetic efficiency, yield, and nutritional quality in sustainable, controlled-environment agriculture.
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