Smart Luminescent Coordination Polymers toward Multimode Logic

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Smart Luminescent Coordination Polymers towards Multimode Logic Gates: Time-resolved, Tribochromic and Excitationdependent Fluorescence/Phosphorescence Emission Yongsheng Yang, Ke-Zhi Wang, and Dongpeng Yan ACS Appl. Mater. Interfaces, Just Accepted Manuscript • Publication Date (Web): 26 Apr 2017 Downloaded from http://pubs.acs.org on April 26, 2017

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ACS Applied Materials & Interfaces

Smart Luminescent Coordination Polymers towards Multi-mode Logic Gates: Time-resolved, Tribochromic and Excitation-dependent Fluorescence/Phosphorescence Emission

Yongsheng Yang,† Ke-Zhi Wang,*,† and Dongpeng Yan*,†‡

†

Beijing Key Laboratory of Energy Conversion and Storage Materials College of

Chemistry, Beijing Normal University, Beijing 100875 (P. R. China) E-mail: [email protected]; [email protected]

‡

State Key Laboratory of Chemical Resource Engineering, Beijing University of

Chemical Technology, Beijing 100029, P. R. China.

ACS Paragon Plus Environment

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ABSTRACT: In this work, we propose that lanthanide cations (such as Eu3+ and Tb3+) doped long-afterglow coordination polymer (CP) can be an effective way to design multi-mode optical logic gates based on their tunable fluorescence/phosphorescence transformation and state-dependent emission. First, multi-color and white-light luminescence across the blue/green/yellow/red visible regions can be obtained by balancing the co-doping ratio of Eu3+/Tb3+ cations and suitable excitations. Additionally, new tribochromic Eu-Cd-CP was developed based on the mechanism of change in structural symmetry. Benefitting from the long-afterglow, tribochromism and excitation-dependent emission on the same luminescent CP, a new three-input and three-output logic gate was obtained. Therefore, this work not only provides detailed insights into the interesting fields of tribochromism and tunable photoemission, but also confirms that long-afterglow CPs can serve as a new platform for the construction of smart luminescent systems and multi-mode optical logic gates. Keywords: coordination polymer, long-afterglow, tribochromism, excitation-dependent emission, optical logic gate


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1. INTRODUCTION Smart luminescent materials have received much attention because of their various potential applications including in photodevices,1-2 sensors,3-4 and optical storages.5-6 In this sense, optical logic gates can be regarded as a combination of independent smart systems with light as output signals.7-8 Furthermore, molecular logic gates have a great potential for developing molecule-scaled optical, electronics, chemical and biological computers, which could be used in the fields of sensing, molecular recognition and diagnosis.9-15 To date, although molecular logic gates have been widely developed, several challenges remain unresolved. For example, compared with the well-documented systems with single or double inputs, the design of multi-mode optical logic gates is a promising trend owing to the multiple controllable units for information security and high-level logic computation. However, such high-efficiency multi-mode logic gates remain limited. In addition, to fabricate practical logic gate devices, it is necessary to construct solid-state logic gates rather than pristine solution systems. Moreover, the logic devices with chemical inputs (such as ions and molecules) usually involve complicated operation processes and suffer from resetting by the accumulation of chemical inputs; thus the design of new facile input signals is highly desirable. Coordination polymers (CPs) are inorganic-organic hybrid materials made from the assembly of metal ions and organic linkers.16-17 CPs have considerable important applications in a wide range of gas storage and separation,18-20 catalysis,21-23 and sensor devices24 owing to their exceptional tenability and structural diversity. Furthermore, fluorescent CPs have received special attention due to their outstanding performance in luminescence and illumination devices.25-26 For example, the lanthanide doped CPs (Ln-CPs) offer the possibility of full-color displays and tunable emission because of their good color purity and high luminescence quantum efficiencies.27-28 Generally, the parity-forbidden f-f transition of lanthanide cations limits their light absorption, and the high-efficiency emission from lanthanide-CP materials usually relies on a suitable antenna ligand. In such a case, the energy levels of the excited species match with the excited 4f-states of lanthanide cations, and the energy can be unobstructed to the lanthanides, thus



allowing the effective 4f-emission.29 Such process is also known as antenna effects30 or luminescence sensitization. Additionally, smart luminescent CPs, which present changes in luminescence under external stimuli (heat, light, pressure, and pH), have also been developed for sensor and detection applications.31 However, how to develop multi-stimuli-responsive photofunctional CPs systems remains a major problem. Very recently, CPs-based long-afterglow room temperature phosphorescence (RTP) materials have been developed,32-34 that present intriguing persistent photoemission on a much longer lifetime scale (lifetime: millisecond to second level) relative to the range of well-established fluorescent CPs systems (lifetime: nanosecond to microsecond level). In principle, the long-afterglow CPs may serve as an effective platform to develop multi-mode solid-state logic gates and multi-smart luminescent materials, based on the following design strategies: (1) the time-dependent luminescent switching from fluorescence to phosphorescence can be a new optical output state before and after the removal of excitation; (2) the doping of red-emitting Eu3+ cations and green-emitting Tb3+ cations into a blue-emitting framework could result in a series of Ln-Cd-CPs with tunable color and white-light emission by controlling the amount of lanthanide cations and modulating the excitation wavelength; and (3) since the energy transfer from the ligand to lanthanide ions as well as the molecular long-afterglow signal are highly dependent on their crystalline and aggregation states, the external perturbation of solid-state CPs (such as grinding or mechanical stimulus) could further alternate their luminescence. Thus, new tribochromic luminescent materials can be developed. Herein, by taking advantage of both prolonged emission performance and the incorporation of lanthanide ions into the hybrids, we have designed Eu3+/Tb3+ cations doped Cd-based persistent long-afterglow CPs, which exhibit tunable excitation-dependent luminescence and tribochromic photoemission. Furthermore, a solid-state CP-based logic gate with three input signals (UV on/off, excitation wavelength (250/340 nm), and state (powder/crystal)) and three output signals (blue, green, and red emission) can be constructed. These logical relationships are shown in Scheme 1, in which three crucial factors combined suitably and eight states involving three emission colors can be obtained. Therefore, this work offers a new strategy to develop smart multi-mode logic gates that are based on long-afterglow


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Ln-Cd-CPs

materials

with

interesting

excitation-dependent

and

tribochromic

luminescence.35-38

Scheme

1.

The

schematic

representations

of

tunable

excitation-dependent

photoluminescence, tribochromism and long-afterglow performance of the Ln-Cd-CPs.

2. Results and Discussion 2.1. Structure and Morphology. The pristine Cd-based CP was hydrothermally synthesized by mixing Cd(NO3)2∙4H2O, 1,3-benzenedicarboxylic acid (m-BDC), and benzimidazole (BIM).39 The Cd-CP crystallizes in the orthorhombic space group Pbcm, and the central metal cation lies exactly on the plane of symmetry. As shown in Figure 1a, the m-BDC ligand serves as a linker to coordinate with four different Cd2+ cations. Each unit is constructed by one cadmium cation, one m-BDC2- and one coordinated water molecule. Then, Ln-Cd-CPs were synthesized by introducing different ratios of Eu3+ and/or Tb3+ cations (mol% = 0.5-1.5%, Table S1) into the systems. Powder X-ray diffraction (XRD) patterns (Figure 1b) for the as-synthesized Ln-Cd-CPs are all in good agreement with that of the pristine Cd-CP, indicating that the incorporation of lanthanide ions does not induce a structural change relative to the pristine Cd-CP. This result can be attributed to their similar cationic radii (0.095, 0.095 and 0.092 nm for Cd2+, Eu3+ and Tb3+, respectively) and the matchable



coordination number (all cations can implement a hepta-coordinated structure), which achieved the partial substitution of Cd2+ cations. To further illustrate homogeneous doping of the lanthanide ions, the single crystal structures of doped CPs have been determined. By comparing the crystallographic data of Ln-Cd-CPs with Cd-CP (Table S2 and S3), we found that the a–axis and b–axis of the unit cell become slightly longer, while the c–axis gets shorter upon doping. The changes of cell parameters can be attributed to that the orderly arrangement of the center metal along a/b axis induces the increase of the strain in the ab plane, and the force between the center metal and ligand was also increased leading to the decrease of the c–axis. FTIR spectra (Figure S1) show that the characteristic absorption peak from the nitrate anion appears at 1380 cm-1, which can be because the partially coordinated water molecule was substituted by the nitrate anion to balance the positive charges after introducing the lanthanide cations. Thermogravimetric analysis (TGA, Figure 1c) and differential scanning calorimetry (DSC, Figure 1d) show that the decomposition temperature of Ln-Cd-CPs was 387 ºC, which was slightly increased compared with that of Cd-CP (383 ºC). The TGA of the CPs all exhibit two weight loss peaks. The initial step from 25 ºC to 240 ºC with weight losses of 6.9% for Cd-CP and 6.1% for Ln-Cd-CPs is attributed to the removal of the terminal water molecule (theoretical value: 6.1%). This is also confirmed by the FT-IR spectra after treating the samples at 240 ºC (Figure S2). There is no obvious weight loss between 240 ºC and 383 (387) ºC. The further weight loss of approximately 49.9% for Cd-CP (approximately 50.7% for Ln-Cd-CP) between 383 (387) and 800 ºC is due to the m-BDC ligand decomposition. The weight of decomposed CP is 43.2% and it can be attributed to CdO (theoretical value: 43.6%). The experimental results show that the thermostability nearly remains the same upon formation of Ln-Cd-CPs.


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Figure 1. The lattice unit (a) with hydrogen atoms omitted for clarity. The PXRD patterns (b), TGA curves (c) and DSC traces (d) for Cd-CP and Ln-Cd-CPs.

To further investigate the surface morphologies and elemental distributions of the Ln-Cd-CPs, scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX) analysis was carried out. For the Eu-Tb-Cd-CP sample, the typical SEM images (Figure S3a) show the well-defined quasi-hexagon crystal of ca. 1 mm in width. The EDS elemental mapping in Figures S3b-d demonstrated that Cd, Eu and Tb compositions are distributed homogeneously within the crystal. The homogeneous distributions of Ln and Cd cations were also confirmed in Eu-Cd-CP and Tb-Cd-CP systems (Figure S4). These results confirm that the lanthanide cations have been well doped into the Cd-CP lattice.

2.2. Luminescent Properties of Eu-Cd-CP Crystals and Powder. The room-temperature solid-state excitation (λem = 400 nm and 615 nm, Figure S5) and photoemission spectra (λex = 250 and 340 nm) of Eu-Cd-CP in powder and crystal states



were studied (Figure 2a). The Eu-Cd-CP displays bright luminescence with a wide band centered at approximately 400 nm when excited by 340 nm UV light for both the powder and crystal states. Upon excitation at 250 nm, the crystal sample maintains broad-band luminescence at ca. 400 nm, which coincides with a ligand-based emission related to the π→π* electron transition. Interestingly, upon grinding the crystal into the powdered form, the ligand-centered emissions are significantly suppressed, and a series of characteristic luminescence peaks belonging to Eu3+ appear at 580, 593, 615, 653 and 703 nm, corresponding to the 5D0→7FJ (J = 0-4) transitions, respectively. Herein, the UV-visible spectra show that the optical characteristics of Cd-CP and Ln-Cd-CPs below 320 nm are very similar with those of m-BDC (π→π* transition of m-BDC ligand, Figure S6). Comparing the excitation spectra (λem = 615 nm) and UV-visible spectra of Eu-Cd-CP, the high degree of their overlap indicates an efficient “antenna effect” from m-BDC: the ligand has the ability to absorb the energy of the UV illumination and transfer into the lanthanide cation, which is otherwise a very weak UV absorber (forbidden f-f transition).40 Based on the observations above, the adjustable photoluminescent properties were obtained by changing the excitation wavelength for the Eu-Cd-CP, and the optimization of excitation wavelengths (the intensity difference of ligand and Eu3+ characteristic peaks in the emission spectra is the largest) for the pristine ligand and Eu3+ active ions are located at 250 and 340 nm, respectively (Figure S5). Furthermore, for the powder state sample, the red emission at 615 nm has the highest intensity, demonstrating that the incorporated Eu3+ ions occupy the sites without an inversion center and have low crystal field symmetry. This is further confirmed by the presence of 580 nm emission since it only appears when the Eu3+ cations symmetry is rather low.41-43 Thus, the symmetry of Eu3+ ions has been reduced after the crystal sample was ground into powder, and such a mechanism can lead to the tribochromic phenomenon, which will be discussed in a later section. When the sample is excited at 340 nm, both the crystal and powder exhibit blue light with color coordinates at (0.25, 0.15) and (0.24, 0.16), respectively. Furthermore, with excitation at 250 nm, the crystal state sample shows blue-violet emission (color coordinates: 0.38, 0.20), while the powder state sample shows red emission (color


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coordinates: 0.58, 0.33) (Figure 2b). Therefore, the photoemission color is highly dependent on the state of the Eu-Cd-CP. To study the room-temperature afterglow behavior of the Eu-Cd-CP, the solid-state phosphorescence emission spectrum was obtained. The Eu-Cd-CP sample exhibits luminescence centered at 510 nm together with emission characteristics of the Eu3+ cation (580, 593, 615, 653 and 703 nm, Figure S7a), which belong to the phosphorescence of the original Cd-CP framework that come from the triplet excited state Cd-m-BDC center,39 and incorporated Eu3+ cations, respectively. Although the former luminescence intensity is weaker than that of the latter one, the phosphorescence lifetime of the Cd-CP framework (454 ms) is much longer than that of active Eu3+ cations (10.54 ms) (Figure S7b-c). Hence, after turn off the UV light source, only the green color afterglow could be traced by the naked eye (Figure S8). The scheme of the spectral transfers for Eu-Cd-CP is summarized in Figure 2c.

Figure 2. (a) Room-temperature solid-state photoluminescent emission spectra (λex = 250 nm and 340 nm) of Eu-Cd-CP in powder and crystal states. (b) Corresponding CIE color coordinates of Eu-Cd-CP. (c) Schematic diagram of the spectral characteristics of Eu-Cd-CP.

2.3. Mechanism of the Tribochromic Luminescence. To better understand the obvious luminescence differences between the powder and crystal state samples, we investigated the possible mechanism of tribochromic luminescence. The transformation from the weak emission into the strong luminescence



of Eu3+ ions demonstrates that after grinding the sample from crystals to powder, the intensity of Eu3+ cations (5D0→7F2 characteristic peak) has been significantly enhanced, which is mainly influenced by the local symmetry of Eu3+ cations and the nature of the ligands.44 XRD patterns show that the (002) diffraction has been largely reduced upon grinding (Figure 3a), illustrating that the long-range ordering in the (001) direction along the c-axis of ligand and metal connection has been decreased, since the crystal internal strain and asymmetry increased during the friction process.45 Additionally, preferential orientation of the crystallites may also influence the change in the intensity of the (002), (004), (006) and (008) peaks in XRD patterns. Furthermore, by carefully observing the emission change upon grinding, we found that the Eu3+ emission initially appeared on the breakage location of a single crystal (Figure 3b and Movie S1). These phenomena also indicate that the friction process has decreased the crystal symmetry and relaxed the selection rules of the forbidden f-f transitions to gain the high intensity of Eu3+ cations (5D0→7F2 characteristic peak). Based on the analysis above, the mechanism of tribochromic luminescence can be summarized. In the crystal state, the intensity of the transition 5D0→7F2 is very weak due to the higher symmetry of the Eu3+ site. During the process of grinding into powder, the symmetry was reduced, and thus the intensity of the transition 5D0→7F2 greatly enhanced, achieving the phenomenon of tribochromic luminescence. The schematic diagram for the tribochromic mechanism of Eu-Cd-CP is shown in Figure S9. To the best of our knowledge, the tribochromic luminescent materials can potentially be used in various applications such as information displays, pressure sensors, and probes.46-48 Over the last decade, various types of organic compounds,49-51 organometallic systems,52-54 liquid-crystals55-57 and polymer materials58-59 have been reported to show changes in the photoluminescence color in response to mechanical simulation. The mechanisms for tribochromic luminescence mainly involve chemical reactions60 or alteration of the molecular packing.61 Recently, Zhou et al have developed a luminescent CP with a grinding-induced emissive shift based on the changes in the intermolecular interactions during the phase transfer.62 Zhang et al have reported a Eu-based CP with a tribochromic luminescence behavior based on the intermolecular charge transfer


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interaction of the ligand.63 However, tribochromic CPs remain very limited. Thus, the system developed in this work may represent the first example of tribochromic luminescence for lanthanide-doped CPs materials based on the mechanism of change in structural symmetry.

Figure 3. (a) XRD patterns of powder and crystal state Eu-Cd-CP. (b) Series of photographs showing the process of tribochromic luminescence. The photographs were taken under ambient conditions and at 254 nm illumination.

2.4. Multi-color and White-light Photoluminescence. As the Eu3+ cations, Tb3+ cations and m-BDC-based CP framework present red, green and blue light emission, respectively, it is desirable to obtain multi-color and white-light emission

by doping

Eu3+

and

Tb3+

cations

into

m-BDC-based

CPs.

The

photoluminescence of different Eu3+/Tb3+ cations doping ratios in the solid-state samples was studied in detail by changing the excitation wavelength. As shown in Figure 4a-c and Figure S10, the Ln-Cd-CPs exhibit two types of emission bands (ligand-based and Ln-based) when varying the excitation wavelengths from 280 nm to 330 nm. The intensity for the ligand-based emission band enhances with an increase in the excitation wavelength. However, the change of the Ln-based emission intensity was divided into the following two parts: upon changing the excitation wavelength from 280 nm to 300 nm, the emission enhances gradually and reaches the maximum, which is then decreased with



increasing the excitation wavelength from 300 to 330 nm. Based on the different change tendencies of two types of emission band intensities, we could balance the blue/green/red components by adjusting the ratios of m-BDC and co-doped Eu3+/Tb3+ cations, and thus a series of multi-color and white-light emissive CPs was obtained. The Commission Internationale de l’Eclairage coordinates64 (CIE, Figure 4d and Figure S11) and Correlated Color Temperature (CCT) of Ln-Cd-CPs were detected to validate the tunable photoluminescence color. The overall color properties of Ln-Cd-CPs powdered samples excited at different wavelengths are summarized in Tables S4 and S5. The samples present tunable multi-color emission from blue to green, yellow and red regions for Tb-Cd-CP, Eu-Cd-CP and Eu-Tb-Cd-CP, respectively. Particularly, the ternary Eu-Tb-Cd-CP, Eu1-Tb2-Cd-CP, Eu2-Tb1-Cd-CP and Eu3-Tb1-Cd-CP systems can exhibit quasi-white-light at certain excitation wavelengths. Taking the Eu-Tb-Cd-CP as an example, the emission excited by 310 nm lies to the yellow side of pure white light with CIE of (0.3718, 0.4031) and a CCT of 4383 K, resulting in the “warm” white light; the emission excited by 320 nm lies to the blue side of pure white light with CIE of (0.2898, 0.3284) and a CCT of 7884 K, resulting in the “cold” white light (Table 1), which are also close to the standard white-light emission with the color coordinates of (0.33, 0.33).65 Thus, their CCT values could transfer between “warm” and “cold” white-light emission. Additionally, the white emission that is a superposition of multiple emissions presents shift to yellow color when the concentrations of doped Eu3+ and Tb3+ cations increase, and the concentration of Eu3+ cations has a greater effect than that of Tb3+. The corresponding emission photographs of Ln-Cd-CPs powder samples excited at 280-330 nm are shown in Figure 4e, confirming that the multi-color and white-light photoluminescence are finely tuned by changing the excitation and Eu3+/Tb3+ ratio.


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Figure 4. Room-temperature solid-state photoluminescent emission spectra of Eu-Cd-CP (a), Tb-Cd-CP (b) and Eu-Tb-Cd-CP (c) under varying excitation wavelengths from 280 nm to 330 nm. (d) Corresponding CIE color coordinates of Eu-Cd-CP, Tb-Cd-CP and Eu-Tb-Cd-CP. (e) Photographs of Ln-Cd-CP powder samples taken under excitation with 280-330 nm light.



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Table 1. The CIE chromaticity coordinates and CCT for quasi-white-light Ln-Cd-CPs powder samples excited at an appropriate wavelength.

Ln-Cd-CPs

ex (nm)

CIE coordinates

CCT (K)

Eu-Tb-Cd-CP

310

(0.3718, 0.4031)

4383

Eu-Tb-Cd-CP

315

(0.3337, 0.3681)

5471

Eu-Tb-Cd-CP

320

(0.2898, 0.3284)

7884

Eu1-Tb2-Cd-CP

315

(0.3715, 0.4004)

4377

Eu1-Tb2-Cd-CP

320

(0.3166, 0.3574)

6183

Eu1-Tb2-Cd-CP

325

(0.2854, 0.3309)

8123

Eu2-Tb1-Cd-CP

320

(0.3559, 0.3319)

4455

Eu2-Tb1-Cd-CP

325

(0.3134, 0.3145)

6566

Eu2-Tb1-Cd-CP

330

(0.2985, 0.3047)

7720

Eu3-Tb1-Cd-CP

320

(0.3366, 0.3136)

5241

Eu3-Tb1-Cd-CP

325

(0.3049, 0.2983)

7345

Eu3-Tb1-Cd-CP

330

(0.2955, 0.2909)

8307

2.5. CPs-based Multi-mode Logic Gates. The optical molecular logic gates commonly employ chemical,66-67 bimolecular68 and/or optical simulations69-70 as inputs and an optical response as the output. In this work, Ln-Cd-CPs were used as the three-input and three-output logic gates, in which time-dependent, excitation-dependent and state-dependent luminescent properties have been introduced as input signals based on the long-afterglow and tribochromic photoemission. We take Eu-Cd-CP as an example to recommend this design strategy towards new optical logic gates. Time-dependent (input 1: UV ON is “1”; UV ON-TO-OFF is “0”), excitation-dependent (input 2: UV light ex = 250 nm is “1”; ex = 340 nm is “0”), and state-dependent (input 3: powder state is “1”; crystal state is “0”) signals are defined as inputs. The normalized intensity values (the ratio of detected intensity to the maximum for each emission wavelength) at 615, 400 and 510 nm are


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defined as O1 (output 1), O2 (output 2) and O3 (output 3), respectively. Since O3 is the signal on the time scale, the detection for this signal intensity is delayed by 100 ms. The normalized intensity threshold for output was set as 0.30, which could distinguish these three output signals effectively. When the normalized intensity is lower than 0.30, the output signal is defined as the OFF state “0”. Otherwise, the output signal corresponds to the ON state “1”. The normalized intensity values of 615, 400 and 510 nm are presented in Figure 5a, which include eight various combinations obtained by three crucial factors.

Figure 5. (a) Normalized intensity outputs of Eu-Cd-CP at 615, 400 and 510 nm with eight various combinations obtained by three crucial factors. Yellow dotted line represents the normalized intensity threshold value. (b) Three-input and three-output logic gate system for Ln-Cd-CPs. For I1, ON= “1” and ON-TO-OFF = “0”; for I2, 250 nm = “1” and 340 nm = “0”; and for I3, powder = “1” and crystal = “0”. For O1, red = “1” and other = “0”; for O2, blue = “1” and other = “0”; and for O3, green = “1” and other = “0”. As shown in Table 2 and Figure 5b, the truth table values for output 1 form an AND logic gate, the values of output 2 form a NAND-AND logic gate, and the values of output 3 form a NOT logic gate. For example, if I1 = 0, no matter if I2 or I3 is “0” or “1” (under conditions turning off UV), the output 3 value will always become 1 (O3 = 1; green light), which is related to the long-afterglow emission for a few seconds after the removal of UV excitation. In the case of I1 = 1, I2 = 1 and I3 = 1 (UV light on (250 nm) and the powder state), the output 1 value will become 1 (O1 = 1; red light). If I1 = 1 and I2 and I3 are not simultaneously in the “1” states (UV light on (340 nm) or the crystal state), the output 2 value will become 1 (O2 = 1; blue light). To the best of our knowledge, such multi-input/output logic gates based on luminescent CPs haves never been reported before



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1 2 3 this work. 4 5 Table 2. Truth table for all of the possible strings of the three-input and three-output logic 6 gate. 7 8 UV ON / normalized normalized normalized ex = 250 nm / powder state / 9UV ON-TO-OFF crystal state intensity (615 nm) intensity (615 nm) intensity (615 nm) ex = 340 nm 10 I1 I2 I3 O1 O2 O3 11 1 1 1 1 (1.000) 0 (0.234) 0 (0.010) 12 13 1 1 0 0 (0.096) 1 (0.593) 0 (0.010) 14 1 0 1 0 (0.039) 1 (1.000) 0 (0.010) 15 1 0 0 0 (0.035) 1 (0.808) 0 (0.010) 16 17 0 1 1 0 (0.010) 0 (0.010) 1 (1.000) 18 0 1 0 0 (0.010) 0 (0.010) 1 (1.000) 19 0 0 1 0 (0.010) 0 (0.010) 1 (1.000) 20 21 0 0 0 0 (0.010) 0 (0.010) 1 (1.000) 22 23 24 25 3. CONCLUSION 26 27 In conclusion, lanthanide ion doped Cd-CPs were fabricated, which present 28 29 excitation-dependent luminescence, tribochromic emission and effective long-afterglow 30 31 properties. By controlling the excitation wavelength and co-doping ratio of Eu3+ and Tb3+ 32 33 cations, the multi-color emission (blue, green, yellow, and red) covering nearly the entire 34 35 visible region as well as “warm” and “cold” white-light emission can be finely tuned. 36 37 Furthermore, new Eu-Cd-CP tribochromic material has been developed by the tuning of 38 the energy transfer process based on the design of central metal cations away from the 39 40 symmetry plane upon external grinding. Taking advantage of the long-lived 41 42 long-afterglow, tribochromic and excitation-dependent luminescence of the Ln-Cd-CPs, 43 44 new solid-state optical logic gates with three inputs and three outputs can be constructed. 45 46 It is expected that the design strategy for the multifunctional coordination polymers could 47 48 be applied to other smart luminescent systems towards solid-state illumination, 49 50 information storage, optical sensors, and memory device applications. 51 52 53 54 55 56 57 58 59 60


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EXPERIMENTAL SECTION All details of experimental procedures are reported in the Supporting Information.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Figure S1 shows the FT-IR spectra of Cd-CP and Ln-Cd-CPs. Figure S2 shows the FT-IR spectra of Cd-CP and Ln-Cd-CPs after treatment at 240 ºC. Figure S3 shows the SEM image of Eu-Tb-Cd-CP with elemental mapping of Cd (b), Eu (c), and Tb(d). Figure S4 shows the SEM image of Eu-Cd-CP with its elemental mapping of Cd and Eu and SEM image of Tb-Cd-CP with its elemental mapping of Cd and Tb. Figure S5 shows the room-temperature solid-state excitation spectra of Eu-Cd-CP. (λem = 400 nm and 615 nm) Figure S6 shows the UV-visible absorption spectra for Cd-CP and Ln-Cd-CPs. Figure S7a shows the normalized phosphorescence spectrum of Eu-Cd-CP, and Figure S7b and c show the emission decay curves at 510 nm and 615 nm for Eu-Cd-CP under ambient conditions. Figure S8 shows the photographs of Ln-Cd-CPs powder samples taken at different time intervals before and after turning off the UV excitation (254 and 365 nm) under ambient conditions. (Choosing the 254 and 365 nm as the excitation wavelength is due to the light of these two bands can be easily obtained by mercury lamp.) Figure S9 shows the schematic mechanism of structural symmetry breaking for the tribochromic luminescence of Eu-Cd-CP. Figure S10 shows the room-temperature solid-state photoluminescent emission spectra of Eu1-Tb2-Cd-CP, Eu1-Tb3-Cd-CP, Eu2-Tb1-Cd-CP and Eu3-Tb1-Cd-CP under different excitation wavelengths from 280 nm to 330 nm. Figure S11 shows the corresponding positions in the color coordinates diagram of Eu1-Tb2-Cd-CP, Eu1-Tb3-Cd-CP, Eu2-Tb1-Cd-CP and Eu3-Tb1-Cd-CP. Table S1 shows the molar ratios of Cd2+, Eu3+ and Tb3+ cations in Cd-CP and Ln-Cd-CPs. Table S2 shows the crystallographic data for Cd-CP and Ln-Cd-CPs. Table S3 shows the lattice parameters and length of coordination bonds for Cd-CP and Ln-Cd-CPs. Table S4 shows the CIE chromaticity coordinates for Ln-Cd-CPs powder samples doped with



different molar ratio of Eu3+ and Tb3+ cations excited with 280-330 nm light. Table S5 shows the correlated color temperature (CCT) for Ln-Cd-CPs powder samples doped with different molar ratio of Eu3+ and Tb3+ cations excited with 280-330 nm light. Movie S1 shows the tribochromic luminescence process of Eu-Cd-CP at 254 nm illumination.

AUTHOR INFORMATION Corresponding Authors E-mail: [email protected] E-mail: [email protected] Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS This work was supported by the 973 Program (Grant No. 2014CB932103), the National Natural Science Foundation of China (Grant No. 21301016 and 21473013), the Beijing Municipal Natural Science Foundation (Grant No. 2152016), the Fundamental Research Funds for the Central Universities, and Analytical and Measurements Fund of Beijing Normal University, Program for Changjiang Scholars and Innovative Research Team in University.

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Smart Luminescent Coordination Polymers toward Multimode Logic

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